Methods for treating lignocellulosic materials

ABSTRACT

The present invention relates to methods of processing lignocellulosic material to obtain hemicellulose sugars, cellulose sugars, lignin, cellulose and other high-value products such as asphalt and bio oils. Also provided are hemicellulose sugars, cellulose sugars, lignin, cellulose, and other high-value products such as asphalt and bio oils.

CROSS-REFERENCE

This application is a Divisional application of U.S. application Ser.No. 14/787,755, filed Oct. 28, 2015, which is a 371 National Stage Entryof PCT Application No. PCT/US2013/068824, filed Nov. 6, 2013, whichclaims the benefit of PCT Application No. PCT/US2013/039585, filed May3, 2013 and U.S. Provisional Application No. 61/839,780, filed on Jun.26, 2013, each incorporated herein by reference in its entirety.

INCORPORATION BY REFERENCE

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each individual publication, patent, or patent application wasspecifically and individually indicated to be incorporated by reference.

FIELD OF THE INVENTION

The invention relates to processing of lignocellulosic biomass materialscontaining lignin, cellulose and hemicellulose polymers.

BACKGROUND OF THE INVENTION

Lignocellulosic biomass materials are renewable sources for productionof amino acids for feed and food supplements, monomers and polymers forthe plastic industry, and renewable sources for different types offuels, polyol sugar substitutes (xylitol, sorbitol, manitols and thelikes), and numerous other chemicals that can be synthesized from C5 andC6 sugars. Nonetheless, efficient and cost effective processes toextract C5 and C6 sugars from the biomass are still a challenge. Afurther challenge is to extract and separate not only the hemicellulosefraction of biomass, but to devise an effective process to also extractand separate the lignin fraction and the cellulose fraction. It isrealized that an economically viable biorefinary needs to be able toextract and valorize all 3 major components of biomass, i.e.hemicellulose, lignin and cellulose.

SUMMARY OF THE INVENTION

The invention provides a lignin composition. The lignin composition ischaracterized by at least one, two, three, four, five, six, seven,eight, nine, ten, eleven, twelve, or thirteen characteristic(s) selectedfrom the group consisting of: (i) lignin aliphatic hydroxyl group in anamount up to 2 mmole/g; (ii) at least 2.5 mmole/g lignin phenolichydroxyl group; (iii) less than 0.40 mmole/g lignin carboxylic hydroxylgroup; (iv) sulfur in an amount up to 1% weight/weight; (v) nitrogen inan amount up to 0.5% weight/weight; (vi) 5% degradation temperaturehigher than 220° C.; (vii) 10% degradation temperature higher than 260°C.; (viii) less than 1% ash weight/weight; (ix) a formula of CaHbOc;wherein a is 9, b is less than 12 and c is less than 3.5; (x) a degreeof condensation of less than 0.9; (xi) a methoxyl content of at least0.8; (xii) an O/C weight ratio of less than 0.4; and (xiii) a glasstransition elevation between first and second heat cycle as measured bydifferential scanning calorimetry according to DIN 53765 in the range of10 to 30° C. Optionally, the composition is characterized by at leasttwo of said characteristics from said group. Optionally, the compositionis characterized by at least three of said characteristics from saidgroup. Optionally, the composition is characterized by at least four ofsaid characteristics from said group. Optionally, the composition ischaracterized by at least five of said characteristics from said group.Optionally, the lignin composition is further characterized by one, two,three, four, five or six, seven, eight, nine, or ten of additionalcharacteristic(s) selected from the group consisting of: (i) less than1% carbohydrate weight/weight; (ii) solubility in DMSO is >100 g/L;(iii) solubility in THF is >35 g/L; (iv) solubility in 0.1 N NaOHaqueous solution is >8 g/L; (v) less than 1% water by weight; (vi) lessthan 1% volatile components at 200° C. by weight; (vii) a sulfurconcentration of less than 0.1% weight/weight; (viii) soluble sugarcontent of less than 1% by weight/weight; (ix) a phosphorusconcentration of less than 100 PPM; and (x) less than 0.1 times theamount of volatile sulfur compounds found in Kraft lignin. Optionally,the lignin is characterized by at least three of said additionalcharacteristics from said group. Optionally, the composition preparedfrom a substrate comprising hardwood. Optionally, the composition isprepared from a substrate comprising softwood. Optionally, thecomposition is prepared from a substrate comprising bagasse. Optionally,the composition comprising the lignin and an organic solvent, forexample an alcohol, a ketone, an aldehyde, an alkane, an organic acidand a furan of 6 carbons or less. Optionally, the organic solvent ismethyl ethyl ketone. Optionally, the composition further comprises lessthan 20% cellulose weight/weight. Optionally, the composition comprisesless than 15% cellulose weight/weight. Optionally, the compositioncomprises less than 5% cellulose weight/weight. Optionally, thecomposition comprises less than 1% cellulose weight/weight. Optionally,the composition comprises ash at a concentration of less than 0.5%weight/weight. Optionally, the composition is provided as fibers.Optionally, the fibers are characterized by lengthwise tubules with atransverse cross-sectional dimension of at least 5 microns. Optionally,the transverse cross-sectional dimension is less than 20 microns.Optionally, the tubules are characterized by an aspect ratio oftransverse cross-sectional dimension to length less than 0.1.Optionally, the aspect ratio is less than 0.025. Further described, is aproduct that comprises the lignin composition described herein and oneor more other ingredients. Optionally, the product is selected from thegroup consisting of: carbon fibers, protective coatings,lignosulfonates, pharmaceuticals, dispersants, emulsifiers, complexants,flocculants, agglomerants, pelletizing additives, resins, adhesives,binders, absorbents, toxin binders, films, rubbers, elastomers,sequestrants, solid fuels, paints, dyes, plastics, wet spun fibers, meltspun fibers and flame retardants. Optionally, the product is selectedfrom the group consisting of: a non woven fabric, a woven fabric,insulation material, sports equipment, automotive parts, airplane orhelicopter parts, boat hulls or portions thereof and loudspeakers.Further described is a composite material comprising a polymer and oneor more materials selected from the group consisting of epoxy resin,polyester, polyvinyl ester and nylon, said polymer reinforced withfibers described herein.

The invention further provides processes of producing high purity ligninfrom a biomass. The method involves (i) removing hemicellulose sugarsfrom the biomass thereby obtaining a lignin-containing remainder;wherein the lignin-containing remainder comprises lignin and cellulose;(ii) contacting the lignin-containing remainder with a lignin extractionsolution to produce a lignin extract and a cellulosic remainder; whereinthe lignin extraction solution comprises a limited-solubility solvent,an organic acid, and water, wherein the limited-solubility solvent andwater form an organic phase and an aqueous phase; and (iii) separatingthe lignin extract from the cellulosic remainder; wherein the ligninextract comprises lignin dissolved in the limited-solubility solvent;and further comprising one, two, three or four additional step(s): (iv)distilling or flash evaporating the lignin extract thereby removing thebulk of the limited-solubility solvent from the lignin extract to obtaina solid lignin; (v) heating the solid lignin thereby removing tracelimited-solubility solvent or water from the solid lignin; (vi) applyinga vacuum to the solid lignin thereby removing trace limited-solubilitysolvent or water from the solid lignin; and (vii) dissolving the solidlignin with an organic solvent to form a resulting solution andseparating the resulting solution from insoluble remainder. Optionally,the removal of the hemicellulose sugars does not remove a substantialamount of the cellulosic sugars. Optionally, the limited-solubilitysolvent and the water in the lignin extraction solution is in a ratio ofabout 1:1. Optionally, the method comprises contacting the ligninextract with a strong acid cation exchanger in the H⁺ form to removeresidual cations thereby obtaining a purified lignin extract.

The invention further provides a lignin composition produced by aprocess of producing high purity lignin from a biomass. The processcomprises (i) removing hemicellulose sugars from the biomass therebyobtaining a lignin-containing remainder; wherein the lignin-containingremainder comprises lignin and cellulose; (ii) contacting thelignin-containing remainder with a lignin extraction solution to producea lignin extract and a cellulosic remainder; wherein the ligninextraction solution comprises a limited-solubility solvent, an organicacid, and water, wherein the limited-solubility solvent and water forman organic phase and an aqueous phase; and (iii) separating the ligninextract from the cellulosic remainder; wherein the lignin extractcomprises lignin dissolved in the limited-solubility solvent.Optionally, the lignin composition is produced by a process that furthercomprises one, two, three, four, or five additional step(s): (iv)contacting the lignin extract with a strong acid cation exchanger toremove residual cations thereby obtaining a purified lignin extract (v)distilling or flash evaporating the lignin extract thereby removing thebulk of the limited-solubility solvent from the lignin extract to obtainsolid lignin; (vi) heating the solid lignin thereby removing tracelimited-solubility solvent or water from the solid lignin; (vii)applying a vacuum to the solid lignin thereby removing tracelimited-solubility solvent or water from the solid lignin; and (viii)dissolving the solid lignin with an organic solvent to form a resultingsolution and separating the resulting solution from insoluble remainder.Optionally, the lignin composition is characterized by at least one,two, three, four, five, six, seven, eight, nine, ten, eleven, twelve,thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, or nineteencharacteristics selected from the group consisting of: (i) ligninaliphatic hydroxyl group in an amount up to 2 mmole/g; (ii) at least 2.5mmole/g lignin phenolic hydroxyl group; (iii) less than 0.40 mmole/glignin carboxylic OH group; (iv) sulfur in an amount up to 1%weight/weight; (v) nitrogen in an amount up to 0.5% weight/weight; (vi)5% degradation temperature higher than 220° C.; (vii) 10% degradationtemperature higher than 260° C.; (viii) less than 1% ash weight/weight;(ix) a formula of C_(a)H_(b)O_(c); wherein a is 9, b is less than 12 andc is less than 3.5; (x) a degree of condensation of less than 0.9; (xi)a methoxyl content of at least 0.8; (xii) an O/C weight ratio of lessthan 0.4; (xiii) a glass transition elevation between first and secondheat cycle according to DIN 53765 in the range of 10 to 30° C.; (xiv)less than 1% carbohydrate weight/weight; (xv) solubility in DMSO is >100g/L; (xvi) solubility in THF is >35 g/L; (xvii) solubility in 0.1 N NaOHaqueous solution is >8 g/L; (xviii) less than 1% water by weight; and(xix) less than 1% volatile components at 200° C. by weight. Theinvention further provides a spinning method. The method involves (a)providing the lignin composition described herein; (b) spinning saidlignin to produce fibers; and (c) de-solventizing said fibers.Optionally, the method further comprises contacting said compositionwith an anti-solvent. Optionally, the method further comprises mixingsaid composition with a synthetic polymeric material. Optionally, thesynthetic polymeric material comprises polyacrylonitrile. Optionally, aratio of lignin:synthetic polymer is ≧1:10. Optionally, a ratio oflignin:synthetic polymer is ≦10:1.

Optionally, the method further comprises carbonizing said fibers toproduce carbon fibers.

The invention further provides a fiber produced by a method describedherein. For instance, a product comprising a fiber described herein.Further provided is a method comprising: (i) providing a lignincomposition described herein and (ii) converting at least a portion oflignin in the composition to a conversion product. Optionally, theconverting comprises treating with hydrogen. Optionally, the convertingcomprises treating with a hydrogen donor. Optionally, the hydrogen donoris selected form formic acid, formate salt, an alcohol. Optionally, thealcohol is isopropanol. Optionally, the method further comprisesproducing hydrogen from lignin. Optionally, the conversion productcomprises at least one item selected from the group consisting ofbio-oil, carboxylic and fatty acids, dicarboxylic acids,hydroxyl-carboxylic, hydroxyl di-carboxylic acids and hydroxyl-fattyacids, methylglyoxal, mono-, di- or poly-alcohols, alkanes, alkenes,aromatics, aldehydes, ketones, esters, phenols, benzene, toluenes, andxylenes. Optionally, conversion product comprises a fuel or a fuelingredient. Optionally, the conversion product comprises para-xylene.

Further described are consumer products produced according to themethods described herein, a consumer product produced from theconversion product or a consumer product containing the conversionproduct as an ingredient or component. Optionally, the product comprisesat least one chemical selected from the group consisting oflignosulfonates, bio-oil, carboxylic and fatty acids, dicarboxylicacids, hydroxyl-carboxylic, hydroxyl di-carboxylic acids andhydroxyl-fatty acids, methylglyoxal, mono-, di- or poly-alcohols,alkanes, alkenes, aromatics, aldehydes, ketones, esters, biopolymers,proteins, peptides, amino acids, vitamins, antibiotics, paraxylene andpharmaceuticals. Optionally, the product comprises para-xylene.Optionally, the product is selected from the group consisting ofdispersants, emulsifiers, complexants, flocculants, agglomerants,pelletizing additives, resins, carbon fibers, active carbon,antioxidants, flame retardant, liquid fuel, aromatic chemicals,vanillin, adhesives, binders, absorbents, toxin binders, foams,coatings, films, rubbers and elastomers, sequestrants, fuels, andexpanders. Optionally, the product is used in an area selected from thegroup consisting of food, feed, materials, agriculture, transportationand construction. Optionally, the product has a ratio of carbon-14 tocarbon-12 of about 2.0×10⁻¹³ or greater. Optionally, the product furthercomprises an ingredient produced from a raw material other thanlignocellulosic material. Optionally, the ingredient from the productdescribed herein and the ingredient produced from a raw material otherthan lignocellulosic material are essentially of the same chemicalcomposition. Optionally, the product comprises a marker molecule at aconcentration of at least 100 ppb. Optionally, the marker molecule isselected from the group consisting of furfural and hydroxy-methylfurfural, 2,3,5 trimethyl furan, products of their condensation, colorcompounds, acetic acid, p-hydroxyphenoxyacetic acid,4-hydroxy-3,5,-dimethoxyphenyl) acetic acid, methylethyl ketone,Methylpropenyl ketone, 3-(2-furyl)-3-penten-2-one,3-methyl-2-penten-4-one, 3,4-dimethyl-4-hexene-one,5-ethyl-5-hexene-3-one, 5-methyl-4-heptene-3-one, o-hydroxyanisole,3-ethyl-4-methyl-3-penten-2-one, 3,4,4-trimethyl-2-cyclohexene-1-one,2′-hydroxy-4′,5′-dimethylacetophenone,1-(4-hydroxy-3-methoxyphenyl)propane methanol, galacturonic acid,dihydroabietic acid, glycerol, fatty acids and resin acids.

The invention further provides a method of producing cellulose from abiomass. The method comprises: (i) removing hemicellulose sugars fromthe biomass thereby obtaining a lignocellulosic remainder; wherein thelignocellulosic remainder comprises lignin and cellulose; (ii)contacting the lignocellulosic remainder with a lignin extractionsolution to produce a lignin extract and a cellulosic remainder; whereinthe lignin extraction solution comprises a limited-solubility solvent,an organic acid, and water, wherein the limited-solubility solvent andwater form an organic phase and an aqueous phase; (iii) separating thelignin extract from the cellulosic remainder; wherein the lignin extractcomprises lignin dissolved in the limited-solubility solvent; and (iv)obtaining cellulosic remainder pulp. Optionally, the cellulosicremainder pulp is converted to a conversion product using a chemicalprocess. Optionally, the conversion product comprises at least onemember selected from the group consisting of halomethylfurfural,hydroxymethylfurfural, furfural, para-xylene, or any combinationthereof. Optionally, the cellulosic remainder pulp is used to produce atexturizer, an anti-caking agent, a fat substitute, an emulsifier, anextender, or a bulking agent.

The invention further provides a cellulose composition. The cellulosecomposition comprises one or more, two or more, three or more, or fouror more of the following characteristics: (i) cellulose to solid ratioof >85% weight/weight; (ii) crystalline cellulose to solid ratio of >50%weight/weight; (iii) lignin to solid ratio up to <10% weight/weight; and(iv) hemicellulose carbohydrate to solid ratio up to <4% weight/weight.Optionally, the composition comprises cellulose at more than 90%weight/weight. Optionally, the composition further comprises one ormore, two or more, three or more, four or more, five or more, or six ormore of the following characteristics: (i) C6 sugars to solid ratioof >70% weight/weight; (ii) glucose to solid ratio of >70%weight/weight; (iii) C5 sugars to solid ratio up to <5% weight/weight;(iv) total sugars to solid ratio of >75% weight/weight; (v) trace Mg,Mn, Na, Zn <10 ppm; and (vi) trace Cu, Fe, K, Al, Cr, <200 ppm.Optionally, the composition further comprises one or more, two or more,three or more, four or more, five or more, or six or more, seven ormore, eight or more, nine or more, ten or more, eleven or more, ortwelve or more of the following characteristics: (i) a loss of dryingfrom 2.0-5.0%; (ii) bulk density of 0.29-0.36 g/cc; (iii) passesmicrocrystalline cellulose identification tests A and B in the FoodChemical Codex (FCC) (5^(th) Ed. 2004), wherein test A) a white opaque,bubble-free dispersion which does not form a supernatant liquid at thesurface is obtained after 100 mL of a dispersion 45 g of cellulose in255 mL water is mixed for 5 minutes in a high-speed power blender(18,000 rpm) is left standing in a 100-mL graduate for 3 hours, andwherein test B) 20 mL of the dispersion is mixed with a few drops ofiodine TS and no purplish to blue or blue color is produced; (iv) degreeof polymerization is of no more than 350 units; (v) pH of 5.5-7.0; (vi)conductivity is not more than 75 μS/cm; (vii) residue on ignition is notmore than 0.05% weight/weight; (viii) water soluble substances are notmore than 12.5 mg/5 g; (viii) ether soluble substances are not more than5.0 mg/10 g; (ix) heavy metals are not more than 0.001% weight/weight;(x) soluble in copper tetrammine hydroxide; (xi) particle size under 250microns is not less than 10% weight/weight; and (xii) particle sizeunder 150 microns is not less than 50% weight/weight. Further providedis a method of producing a conversion product, wherein the conversionproduct is a texturizer, an anti-caking agent, a fat substitute, anemulsifier, an extender, thin layer chromatography stationary phase,filler in a drug tablet, a bulking agent in food production, plaqueassay kit, or surfactant made from the cellulose composition describedherein. Optionally, the conversion product has a ratio of carbon-14 tocarbon-12 of about 2.0×10⁻¹³ or greater.

The invention further provides methods of producing bio oil from abiomass, comprising: (i) removing ash from the biomass in an ash removalprocess; (ii) removing hemicellulose sugars from the biomass therebyobtaining a lignocellulosic remainder; wherein the lignocellulosicremainder comprises lignin and cellulose; and (iii) producing bio-oil bythermal or hydrothermal conversion of the lignocellulosic remainder.Further provided is the bio-oil produced from the method describedherein.

The invention further provides a method to improve properties of anasphalt composition by compounding the asphalt compound with a least 2%wt/wt solid lignin made using the method described herein, whereimproved properties are selected from one or two or three of thefollowing characteristics: (i) stability against oxidation; (ii)stability against UV radiation; (iii) having a renewable carboncomponent.

Further provided is an annual crop lignocellulosic compositioncomprising less than 4% ash following an ash removal process, whereinsaid annual crop lignocellulosic comprises more than 8% ash at harvestor before ash removal process. Optionally, the annual croplignocellulosic comprises less than 3% ash following an ash removalprocess.

DESCRIPTION OF THE FIGURES

FIGS. 1-4 are simplified flow schemes of methods for treatinglignocellulose material according to some embodiments of the invention.

FIG. 5 is a schematic representation of an exemplary method of treatinglignocellulosic biomass material according to some embodiments of thepresent invention.

FIG. 6 is a simplified flow scheme of a method according to alternativelignin solubilization embodiments of the invention. PPTTP stands for“predetermined pressure-temperature-time profile.”

FIG. 7 is a simplified flow scheme of a method according to someexemplary lignin conversion processes.

FIG. 8A is a simplified flow schemes of method for treating cellulosepulp and residual lignin according to some embodiments of the invention;FIG. 8B shows glucose concentration in the solution at differentstarting cellulose pulp load in the reactor (10-20% wt dry solid); FIG.8C illustrates comparative saccharification of cellulose pulp obtainedby hemicelluloses extraction followed by acid/solvent lignin extraction(E-HDLM), and a commercial Sigmacell cotton linters.

FIG. 9 is a simplified flow scheme of a method according to alternativelignin solubilization embodiments of the invention.

FIG. 10A and FIG. 10B are a schematic representation of an exemplarymethod of treating lignocellulosic biomass material according to someembodiments of the present invention.

FIG. 11 is a series of ³¹P NMR spectra of derivatized lignincompositions: A—comparative sample Kraft lignin; B—lignin made frompine; C—lignin made from bagasse; D—lignin made from eucalyptus

FIG. 12A is a low sensitivity GCMS chromatogram of lignin derived frompine wood.

FIG. 12B is a high sensitivity GCMS chromatogram of lignin derived frompine wood.

FIG. 13A is a low sensitivity GCMS chromatogram of lignin derived fromBagasse.

FIG. 13B is a high sensitivity GCMS chromatogram of lignin derived fromBagasse.

FIG. 14A is a low sensitivity GCMS chromatogram of lignin derived fromEucalyptus.

FIG. 14B is a high sensitivity GCMS chromatogram of lignin derived fromEucalyptus.

DETAILED DESCRIPTION OF THE INVENTION Introduction

The present invention relates to lignocellulosic biomass processing andrefining to produce hemicellulose sugars, cellulose sugars, lignin,cellulose and other high-value products.

An overview of the lignocellulosic biomass processing and refiningaccording to embodiments disclosed herein is provided in FIG. 5. Ingeneral, the lignocellulosic biomass processing and refining processesinclude: (1) pretreatment 1770; (2) hemicellulose sugar extraction 1700and purification 1710; and (3) direct lignin extraction 1760.

Various products can be made using these processes. For example,hemicellulose sugar extraction 1700 produces an aqueous stream ofhemicelluloses 1700-A and a lignocellulose remainder product 1700-P1.Purification 1710 produce a hemicellulose sugar mixture, xylose, and axylose-removed hemicellulose sugar mixture, as well as bioenergypellets. Direct lignin extraction 1760 process produces a high puritylignin. The lignocellulose remainder 1770-P1 can be pelletized as is tomake bioenergy pellet 1700-P2, or can be the substrate for thermal orhydrothermal conversion to bio oil and aromatics. Direct ligninextraction 1760 process produces a high purity lignin and cellulose.This remaining cellulose pulp may be used in any application known ofmicrocrystalline cellulose, including but not limited to a texturizer,an anti-caking agent, a fat substitute, an emulsifier, an extender, thinlayer chromatography stationary phase, filler in a drug tablet, abulking agent in food production, plaque assay kit, or surfactant. Thiscellulose may be hydrolyzed 1820 to high purity glucose, or may bepartially hydrolyzed by selectively hydrolyzing only amorphous celluloseto obtain crystalline cellulose and high purity glucose. Alternativelythe cellulose may be converted to substituted furans by any processknown to convert cellulose to substituted furans; these substitutedfurans may be further converted to para xylene.

The lignocellulosic biomass processing and refining begins withpretreatment 1770, during which the lignocellulosic biomass can be, forexample, debarked, chipped, shredded, dried, or grinded to particles.

During hemicellulose sugar extraction 1700, the hemicellulose sugars areextracted from the lignocellulosic biomass, forming an acidichemicellulose sugar stream 1700A and a lignocellulosic remainder stream1700B. The lignocellulosic remainder stream 1700B consists of mostlycellulose and lignin. Hemicellulose sugars can be effectively extractedand converted into monomeric sugars (e.g., >90% of the total sugar) bytreating biomass under mild conditions, e.g., with an acid in lowconcentrations, heat, and optionally pressure.

The acidic hemicellulose sugar stream 1700-A is purified inhemicellulose sugar purification 1710, acids and impurities co-extractedwith hemicellulose sugars can be easily removed from the hemicellulosesugar stream by solvent extraction. Once acids and impurities areremoved from the hemicellulose sugar stream, the stream is neutralizedand optionally evaporated to a higher concentration. A high purityhemicellulose sugar mixture 1710-P1 is obtained, which can befractionated to obtain xylose and xylose-removed hemicellulose sugarmixture 1710-P3. Xylose is then crystallized to obtain xylose 1710-P2.

The lignocellulosic remainder 1700-B contains mostly cellulose andlignin. In some methods, the lignocellulosic remainder 1700-B can beprocessed to make bioenergy pellets 1700-P, which can be burnt as fuels.

In some methods, the lignocellulosic remainder 1700-P1 can be directlyprocessed to bio-oil by any suitable process selected from pyrolysis,fast pyrolysis, catalytic pyrolysis, hydrothermal pyrolysis,supercritical or sub-supercritical pyrolysis. Bio-oil has the advantageover bio energy pellets of being a liquid phase fuel, and it allowsfurther upgrading by hydrogenation processes to higher quality fuel.Alternatively, some thermal and/or hydrothermal processes utilizingcatalyst(s) may produce directly upgraded fuels. In some methods, thelignocellulosic remainder 1700-P1 is catalytically converted to biofuel,aromatic, and olefin compounds.

Any process that can covert biomass to fuel benefits from using thelignocellulosic remainder as feedstock since hemicelluloses sugarextraction process 1700 removes not only cellulose from the biomass butalso a significant part of ash elements present in the feedstock, hencemaking it a higher grade starting material for said conversionprocesses.

In some methods, the lignocellulosic remainder 1700-P1 can be directlyprocessed to extract lignin. This process produces a high purity lignin1760-P1 and a high purity cellulose 1760-P2. The novel ligninpurification process of the invention utilizes a limited-solubilitysolvent, and can produce a lignin having a purity greater than 99%.

The cellulose product 1760-P2 comprises low levels of lignin, typicallyless than 10%, 8%, 5% wt/wt, and low levels of hemicelluloses, typicallyless than 8%, 5%, 2.5% wt/wt. It may be used in any application thatrequires microcrystalline cellulose.

The cellulose product 1760-P2 can be used as starting material forseveral chemical or biochemical processes. Cellulose 1760-P2, which isprincipally cellulose pulp 1001 FIG. 8A, comprising residual amount oflignin is hydrolyzed by biochemical or chemical saccharification method1002. It is then filtered, purified and fractionated to obtain highpurity glucose product stream as schematically described in FIG. 8A toobtain refined C₆ sugar product, denoted as high purity glucose 1720-P1in FIG. 10B.

In some methods, cellulose product 1760-P2 is converted to substitutedfurans. In some method, this conversion is carried out in a multiphasereactor where gaseous HCl is the catalyst. In other methods thisconversion is carried out in an aqueous solution with magnesium,calcium, aluminum or zinc halide as catalyst. Other metal halides mayalso serve as catalysts. Alternatively boronic acid is employed ascatalyst. In some methods, this conversion is carried out in ionicliquid or in aprotic polar solvent or in a mixture thereof. Conversionmay be assisted by microwave irradiation or by ultrasonic irradiation.

The sections I-VI below illustrate lignocellulosic biomass processingand refining according to some embodiments disclosed herein. Section Idiscusses pretreatment 1770. Section II discusses hemicellulose sugarextraction 1700 and section III discusses conversion of hemicellulosesdepleted lignocellulose remained to bio-oil and upgraded product.Section IV discusses direct lignin extraction 1760 and provides a lignincomposition produced by the processes. Section V discusses uses of thedisclosed lignin composition for making carbon fibers and as feed forconversion processes. VI discloses a method to produce remaindercellulose pulp and composition of remainder cellulose pulp. Section VIIdetails conversion processes of the cellulose pulp.

I. Pretreatment

Prior to hemicellulose sugar extraction 1700, lignocellulosic biomasscan be optionally pre-treated. Pretreatment refers to the reduction inbiomass size (e.g., mechanical breakdown or evaporation), which does notsubstantially affect the lignin, cellulose and hemicellulosecompositions of the biomass. Pretreatment facilitates more efficient andeconomical processing of a downstream process (e.g., hemicellulose sugarextraction). Preferably, lignocellulosic biomass is debarked, chipped,shredded and/or dried to obtain pre-treated lignocellulosic biomass.Pretreatment can also utilize, for example, ultrasonic energy orhydrothermal treatments including water, heat, steam or pressurizedsteam. Pretreatment can occur or be deployed in various types ofcontainers, reactors, pipes, flow through cells and the like. In somemethods, it is preferred to have the lignocellulosic biomass pre-treatedbefore hemicellulose sugar extraction 1700. In some methods, nopre-treatment is required, i.e., lignocellulosic biomass can be useddirectly in the hemicellulose sugar extraction 1700.

In some cases the lignocellulosic biomass comprises up to 10%, up to 15%up to 20% inorganic particles, e.g. small soil particles that adhere tothe growing plant and get encapsulated by the plant tissue such thatthese soil particle that are associated with the biomass and do not getwashed if the biomass is not broken up. Typically sugar cane bagasse,corn stover, rice husks and other annual crops may have such highpercentage of inorganic matter associated with the biomass. To allowutilization of such lignocellulose biomass it is essential to removethis access inorganic matter. Pretreatment may include initial grindingof the biomass and washing of the inorganic matter. The inorganic matteris mostly insoluble at neutral pH, therefore differences in densitiesbetween the small soil particles and the lignocellulosic biomass areutilized to separate between them.

Optionally, lignocellulosic biomass can be milled or grinded to reduceparticle size. In some embodiments, the lignocellulosic biomass isground such that the average size of the particles is in the range of100-10,000 micron, preferably 400-5,000, e.g., 100-400, 400-1,000,1,000-3,000, 3,000-5,000, or 5,000-10,000 microns. In some embodiments,the lignocellulosic biomass is ground such that the average size of theparticles is less than 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000,3,000, 1,000, or 400.

II. Hemicellulose Sugar Extraction

The present invention provides an advantageous method of extractinghemicellulose sugars from lignocellulosic biomass (hemicellulose sugarextraction 1700). Preferably, an aqueous acidic solution is used toextract lignocellulose biomass. The aqueous acidic solution can containany acids, inorganic or organic. Preferably, an inorganic acid is used.For example, the solution can be an acidic aqueous solution containingan inorganic or organic acid such as H₂SO₄, H₂SO₃ (which can beintroduced as dissolved acid or as SO₂ gas), HCl, and acetic acid. Theacidic aqueous solution can contain an acid in an amount of 0 to 2% acidor more, e.g., 0-0.2%, 0.2-0.4%, 0.4-0.6%, 0.6-0.8%, 0.8-1.0%, 1.0-1.2%,1.2-1.4%, 1.4-1.6%, 1.6-1.8%, 1.8-2.0% or more weight/weight.Preferably, the aqueous solution for the extraction includes 0.2-0.7%H₂SO₄ and 0-3,000 ppm SO₂. The pH of the acidic aqueous solution can be,for example, in the range of 1-5, preferably 1-3.5.

In some embodiments, an elevated temperature or pressure is preferred inthe extraction. For example, a temperature in the range of 100-200° C.,or more than 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C.,120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C.,or 200° C. can be used. Preferably, the temperature is in the range of110-160° C., or 120-150° C. The pressure can be in the range of 1-10mPa, preferably, 1-5 mPa. The solution can be heated for 0.5-5 hours,preferably 0.5-3 hours, 0.5-1 hour, 1-2 hours, or 2-3 hours, optionallywith a cooling down period of one hour.

Impurities such as ash, acid soluble lignin, fatty acids, organic acidssuch as acetic acid and formic acid, methanol, proteins and/or aminoacids, glycerol, sterols, rosin acid and waxy materials can be extractedtogether with the hemicellulose sugars under the same conditions. Theseimpurities can be separated from the aqueous phase by solvent extraction(e.g., using a solvent containing amine and alcohol).

After the hemicellulose sugar extraction 1700, the lignocellulosicremainder stream 1700-B can be separated from the acidic hemicellulosesugar stream 1700-A by any relevant means, including, filtration,centrifugation or sedimentation to form a liquid stream and a solidstream. The acidic hemicellulose sugar stream 1700-A containshemicellulose sugars and impurities. The lignocellulosic remainderstream 1700-B contains predominantly cellulose and lignin.

The lignocellulosic remainder stream 1700-B can be further washed torecover additional hemicellulose sugars and acidic catalyst trappedinside the biomass pores. The recovered solution can be recycled back tothe acidic hemicellulose sugar stream 1700-A, or recycled back to thehemicellulose sugar extraction 1700 reactor. The remaininglignocellulosic remainder stream 1700-B can be pressed mechanically toincrease solid contents (e.g., dry solid contents 40-60%). Filtrate fromthe pressing step can be recycled back to the acidic hemicellulose sugarstream 1700-A, or recycled back to the hemicellulose sugar extraction1700 reactor. Optionally, the remaining lignocellulosic remainder 1700-Bis ground to reduce particle sizes. Optionally, the pressedlignocellulosic remainder is then dried to lower the moisture content,e.g., less than 15%. The dried matter can be further processed toextract lignin and cellulose sugars (processes 1720 and 1760 in FIG. 5).Alternatively, the dried matter can be pelletized into pellets 1700-P,which can be burnt as energy source for heat and electricity productionor can be used as feedstock for conversion to bio oil.

Alternatively, the lignocellulosic remainder stream 1700-B can befurther processed to extract lignin (process 1760 in FIG. 5). Prior tothe lignin extraction, the lignocellulosic remainder stream 1700-B canbe separated, washed, and pressed as described above.

It was found that hemicellulose sugar extraction 1700 can produce, inone single extraction process, a hemicellulose sugar stream containingat least 80-95% monomeric sugars. For example, the hemicellulose sugarstream can contain more than 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%,96%, 97%, 98%, or 99% monomeric sugars. In addition, the present methodproduces minimal amounts of lignocellulose degradation products such asfurfural, levulinic acid, and formic acid. In addition, a xylose yieldgreater than 93% of theoretical value can be achieved. Overall, 18-27%of total sugars and at least 70%, 75%, or 80% or more of thehemicellulose sugars can be extracted using the present method.

The acidic hemicellulose sugar stream 1700-A is then subject tohemicellulose sugar purification 1710. Various hemicellulose sugarproducts can be obtained from the purification. Exemplary purifiedproducts include hemicellulose sugar mixture 1710-P1, xylose 1710-P2,and xylose-removed hemicellulose sugar mixture 1710-P3.

Further processing of the hemicelluloses sugar stream is detailed in PCTUS2013/039585, the entire contents of which are incorporated byreference herein. Sections I-VIII of PCT US2013/039585 illustratelignocellulosic biomass processing and refining according to someembodiments, section I discusses pretreatment 1770, sections II and IIIdiscuss hemicellulose sugar extraction 1700 and purification 1710,sections IV and V discuss cellulose hydrolysis 1720 and cellulose sugarrefining 1730, section VI and VII discuss lignin processing 1740 andrefining 1750, and section VIII discusses direct lignin extraction 1760,the contents of these sections are specifically incorporated byreference herein.

III. Applications of Lignocellulose Remainder

Different technologies to convert biomass are being developed. Theseinclude pyrolysis, fast pyrolysis, catalytic pyrolysis, hydrothermalpyrolysis, supercritical or sub-supercritical pyrolysis that convertbiomass to bio-oil. Bio-oil is then upgraded to more stable, high energycontent hydrocarbon compounds. In some technologies, both process stepsare conducted in concert.

Fast pyrolysis, which can involve, for example, rapidly heating biomass(e.g., ˜500° C./sec) to intermediate temperatures (e.g., ˜400-600° C.)followed by rapid cooling (e.g., residence times 1-2 s). (See, A. V.Bridgwater, Review of fast pyrolysis of biomass and product upgrading,Biomass and Bioenergy, 38 (2012) 68-94.). Various designs of reactorsand systems are described, particularly several types of fluidized bedreactor including but not limited to bubbling fluidized bed reactors,circulating fluidized bed reactors, rotary cone reactors, Auger reactorsand ablative reactors. The main difference among these reactors is theapplied heat transfer method which may be by gas, liquid or solid, andthe heating rates which differs in the rang 700-1500 K/s.

The products of fast pyrolysis are char (solid), liquid and a gaseousfraction, control of the heating rate is the major factor controllingthe relative part of the fractions.

Fast pyrolysis often produces a thermally unstable liquid productmixture called bio-oils, an acidic combustible liquid mixture of morethan 300 compounds that degrades with time. The bio-oil mixture can beupgraded to a more stable mixture comprising benzene, toluene, xylene(BTX), along with numerous other chemicals that can be fractionated bydistillation similar to petrochemical distillation and are thereforeconsidered as drop in fuels. Chemically, the upgrading process typicallyinvolves hydrogenation to increase the energy content of the moleculesand remove oxidized molecular moieties. These processes require a sourceof hydrogen, whether supplied or produced in situ in a tandem process,and catalyst(s).

Biomass can be pyrolyzed to one or more fluid hydrocarbon products froma solid hydrocarbonaceous material by reacting it over a solid catalystin a fluidized bed reactor; feeding a solid hydrocarbonaceous materialto the fluidized bed reactor at a mass-normalized space velocity ofbetween about 0.01 hour⁻¹ and about 10 hour⁻¹; pyrolyzing within thefluidized bed reactor at least a portion of the hydrocarbonaceousmaterial under reaction conditions sufficient to produce one or morepyrolysis products; and catalytically reacting at least a portion of theone or more pyrolysis products using the solid catalyst under reactionconditions sufficient to produce the one or more fluid hydrocarbonproducts. Preferred catalyst comprises zeolite catalyst. Preferredproducts of this process are aromatic compounds comprise benzene,toluene, xylenes, substituted benzenes, indanes and naphthalene, and theolefin compounds ethene, propene, and/or butene.

In another process to produce bio-oil from lignocellulose biomass themethod comprising the steps of: (a) fractionating hemicellulose from thebiomass with a solvent, (b) removing fractionated hemicellulose frombiomass remaining after step (a); (c) fractionating either of: (i)lignin (ii) cellulose from the biomass remaining after step (a); and (d)solvating either or both of the lignin and cellulose of step (c),wherein the solvating in step (d) produces the bio-oil product. In oneaspect, the fractionating in step (c) is performed using an alcohol, anaqueous alcohol, or water. The alcohol, aqueous alcohol, or water may beused to fractionate the lignin or cellulose under supercriticalconditions.

The lignocellulose remainder of this invention is an advantageousfeedstock material for the pyrolysis processes described briefly hereinas well as any other biomass pyrolysis process over the native biomassfor several reasons: (i) reduced ash fraction due to removal ofinorganic compounds in the hemicelluloses sugar extraction step, thusreducing amounts of ash produces as byproduct in pyrolysis and reducingcatalysts fouling by inorganic ions; (ii) the lignocellulose remainderis much more amenable to size reduction of compared to native biomassdue to its brittleness, thus reduced energy demands of the sizereduction step; and (iii) increased energy density of the lignocelluloseremainder compared to native biomass due to removal of inorganiccompounds and removal of hemicellulose component.

IV. Direct Lignin Extraction from Lignocellulosic Biomass

The present disclosure includes, in one aspect, a method of extractinglignin directly from lignocellulosic biomass after hemicellulose sugarsare extracted. Such method utilizes a limited-solubility solvent. Suchmethod may be utilized with biomass particles without the need to grindthe particles prior to lignin extraction.

The extraction of hemicellulose sugars from the biomass results in alignin-containing remainder. In some methods, the extraction ofhemicellulose sugars does not remove a substantial amount of thecellulosic sugars. For example, the extraction of hemicellulose sugarsdoes not remove more than 1, 2, 5, 10, 15, 20, 30, 40, 50, 60%weight/weight cellulose. In some embodiments, the lignin-containingremainder contains lignin and cellulose. In some embodiments, thelignin-containing remainder contains less than 50, 45, 40, 35, 30, 25,20, 15, 10, 5, 2, 1% hemicellulose. In some embodiments, the lignin canbe directly extracted from lignocellulosic biomass without removinghemicellulose sugars.

The lignin extraction solution preferably contains a limited-solubilitysolvent, an acid, and water. Examples of limited-solubility solventssuitable for the present invention include methylethylketone,diethylketone, methyl isopropyl ketone, methyl propyl ketone, mesityloxide, diacetyl, 2,3-pentanedione, 2,4-pentanedione, 2,5-dimethylfuran,2-methylfuran, 2-ethylfuran, 1-chloro-2-butanone, methyl tert-butylether, diisopropyl ether, anisol, ethyl acetate, methyl acetate, ethylformate, isopropyl acetate, propyl acetate, propyl formate, isopropylformate, 2-phenylethanol, toluene, 1-phenylethanol, phenol, m-cresol,2-phenylethyl chloride, 2-methyl-2H-furan-3-one, γ-butyrolactone,acetal, methyl ethyl acetal, dimethyl acetal, morpholine, pyrrol,2-picoline, 2,5-dimethylpyridine. Optionally, the limited-solubilitysolvent includes one or more of esters, ethers and ketones with 4 to 8carbon atoms. For example, the limited-solubility solvent can includeethyl acetate. Optionally, the limited-solubility solvent consistsessentially of, or consists of, ethyl acetate.

The ratio of the limited-solubility solvent to water suitable forcarrying out the lignin extraction can vary depending on the biomassmaterial and the particular limited-solubility solvent used. In general,the solvent to water ratio is in the range of 100:1 to 1:100, e.g.,50:1-1:50, 20:1 to 1:20, and preferably 1:1.

Various inorganic and organic acids can be used for lignin extraction.For example, the solution can contain an inorganic or organic acid suchas H₂SO₄, HCl, acetic acid and formic acid. The acidic aqueous solutioncan contain 0 to 10% acid or more, e.g., 0-0.4%, 0.4-0.6%, 0.6-1.0%,1.0-2.0%, 2.0-3.0%, 3.0-4.0%, 4.0-5.0% or more. Preferably, the aqueoussolution for the extraction and hydrolysis includes 0.6-5%, preferably1.2-1.5% acetic acid. The pH of the acidic aqueous solution can be, forexample, in the range of 0-6.5.

Elevated temperatures and/or pressures are preferred in ligninextraction. For example, the temperature of lignin extraction can be inthe range of 50-300° C., preferably 160 to 220° C., e.g., 170-200° C.The pressure can be in the range of 1-30 mPa, preferably, 12-26 mPa. Thesolution can be heated for 0.5-24 hours, preferably 1-3 hours.

Lignin is extracted in the limited-solubility solvent (organic phase),the remaining solid contains mostly cellulose. After the solid phase iswashed to remove residual lignin, the cellulose can be used to producepulp, or as starting material for hydrolysis (acidic or enzymatic).Cellulose may also be hydrolyzed by any acidolysis method known, using amineral acid or an organic acid.

Optionally, the pH of the solvent is adjusted to 3.0 to 4.5 (e.g.,3.5-3.8). At this pH range, the lignin is protonated and is easilyextracted into the organic phase. The organic phase comprising solventand lignin is contacted with strong acid cation exchanger to removeresidual metal cations. To obtain high purity solid lignin, thelimited-solubility solvent is separated from lignin, e.g., evaporated.Preferably, the limited-solubility solvent can be separated from ligninby mixing the solvent solution containing acidic lignin with water at anelevated temperature, optionally under vacuum (e.g., 50-80° C.). Theprecipitated lignin can be recovered by, e.g., filtration orcentrifugation. The solid lignin can be dissolved in any suitablesolvents (e.g., phenylethyl alcohol) for making lignin solutions.

Alternatively, the limited-solubility solvent solution containing acidiclignin can be mixed with another solvent (e.g., toluene). Thelimited-solubility solvent can be evaporated whereas the replacementsolvent (e.g., toluene) stays in the solution. A lignin solution in adesired solvent can be prepared.

FIG. 9 is a schematic description of a process for acid-solventextraction of lignin from hemicellulose depleted lignocellulose matterand for the refining of the solvent-soluble lignin according to certainembodiments of the invention. This process results in stream 200,comprising the solvent and dissolved lignin, where residual ash is lessthan 1000 ppm, preferably less than 500 ppm, wherein polyvalent cationsare less than 500 ppm, preferably less than 200 ppm relative to lignin(on dry base) and residual carbohydrate is less than 500 ppm relative tolignin (on dry base). The solution is free of particulate matter.

The lignin composition derived from direct solvent extraction oflignocellulosic biomass can be further manipulated to furnish a lignincomposition (1760-P1) with desirable traits, fewer impurities, and/orimproved physical characteristics.

The process described herein may further comprise contacting the ligninextract with a strong acid cation exchanger to remove residual cationsthereby obtaining a purified lignin extract. A lignin stream can bepassed through a cation exchanger to further remove residual cations toproduce a lignin product with a concentration of metal cations less than1000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 10 ppm.

The process described herein may further comprise obtaining the ligninas a solid by removing the bulk of the limited-solubility solvent fromthe lignin extract. The bulk of the solvent can be removed bydistillation. The distillation can be achieved by heating the ligninsolution to a temperature near or above the boiling point of the solventunder standard atmospheric pressure. The distillation can be achieved bylowering the pressure for instance by applying a vacuum. The lignin canbe obtained as high purity solid by flash evaporation of the solvent andacid by dripping the organic phase into a water solution heated to atemperature high enough to cause the immediate evaporation of theorganic solvent, i.e. its boiling point and also partial solubility inthe hot water at a low enough level that lignin precipitates. Thetemperature is maintained as low as possible to prevent the lignin fromreacting while the solvent is evaporating. Solvent evaporation may beassisted by applying vacuum in addition to heat. Preferably, flashevaporation is conducted at a temperature of 80 to 95° C., 80-85° C.,50-60° C., or at approximately 55° C. for example.

The process described herein can further comprise a purification of thesolid lignin. In some embodiments, the solid lignin can be furtherpurified by removing trace volatile components from the solid ligninsuch as limited solubility solvent, water, and acid. The trace volatilecomponents can be removed by applying a vacuum to the solid lignin, byheating the solid lignin or by heating the composition and applying avacuum. In some embodiments, the solid lignin can be further purified bydecreasing ash contents from the solid lignin. The ash contents can bedecreased by washing the solid lignin with dilute HCl solution or water.

The process described herein can further comprise one or more additionalsolvent extraction steps. For example, the process can further comprisedissolving the solid lignin with an organic solvent (e.g., methanol ordichloromethane) to form a resulting solution and separating theresulting solution from insoluble remainder. The resulting solution canbe used as pure lignin product stream. The resulting solution can thenbe further evaporated to yield a solid lignin composition lacking theinsoluble remainder.

In some embodiments, the process to produce high purity lignin from abiomass described herein produces a lignin dissolved in thelimited-solubility solvent and further comprises one or more, two ormore, three or more, four or more, or five of the following steps: (i)contacting the lignin extract with a strong acid cation exchanger toremove residual cations thereby obtaining a purified lignin extract (ii)optionally distilling or flash evaporating the lignin extract therebyremoving the bulk of the limited-solubility solvent from the ligninextract to obtain solid lignin; (iii) heating the solid lignin therebyremoving trace limited-solubility solvent or water from the solidlignin; (iv) applying a vacuum to the solid lignin thereby removingtrace limited-solubility solvent or water from the solid lignin; and (v)dissolving the solid lignin with an organic solvent to form a resultingsolution and separating the resulting solution from insoluble remainder.

In some embodiments, the purified lignin extract in limited solubilitysolvent is used as feed for a chemical conversion, avoiding the costassociated with distillation or evaporation systems and operation. Suchsolution of highly purified lignin in solvent is fed into a conversionprocess to convert lignin to conversion products.

Downstream Processing

Exemplary Anti-Solvent Processing:

In some embodiments, an anti-solvent is used for desolventization. Forexample, methyl-ethyl ketone (MEK) has a solubility of 27.5 gram in 100gram aqueous solution (the acidic lignin dissolved in alimited-solubility solvent which is MEK in this embodiment). In someembodiments, spraying lignin dissolved in MEK into water (e.g. atambient temperature) dissolves the MEK in the water. The solubility oflignin in the MEK water mixture (at appropriate water:MEK ratio) is lowso that lignin precipitates. In some embodiments, MEK is separated fromthe mixture by distilling its azeotrope (73.5° C., 89% MEK).

Each solvent/anti-solvent combination represents an additionalembodiment of the invention. Exemplary solvent/anti-solvent combinationsinclude MEK-water; MEK-decanol and MEK-decane.

Exemplary Processing by Distillation:

In some embodiments limited-solubility solvent (e.g. MEK; boilingpoint=79.6° C.) is distilled away from the lignin dissolved in it. Insome embodiments, the distillation includes contacting thelimited-solubility solvent with lignin dissolved in it with a hot gas(e.g. spray drying). Optionally contacting with a hot gas is conductedafter a pre-evaporation which increases the lignin concentration in thelimited-solubility solvent. In some embodiments, the distillationincludes contacting the limited-solubility solvent with lignin dissolvedin it with a hot liquid. In some embodiments, the contacting includesspraying the limited-solubility solvent with lignin dissolved in it intoa hot liquid (optionally after some pre-concentration). In someembodiments, the hot liquid includes water and/or oil and/or Isopar K.In some embodiments, the hot liquid includes an anti-solvent. In someembodiments, the distillation includes contacting the limited-solubilitysolvent with lignin dissolved in it with a hot solid surface.

In some embodiments, a hot liquid is contacted with thelimited-solubility solvent with lignin dissolved in it.Hydrophilic/hydrophobic properties of the hot liquid affect the surfaceproperties of the separated solid lignin. In some embodiments, in thosedistillation embodiments which employ contacting the limited-solubilitysolvent with lignin dissolved in it with a hot liquid, the chemicalnature of the lignin solvent affects the surface properties of theseparated solid lignin. In some embodiments, the hot liquid influencesthe nature and availability of reactive functions on the separated solidlignin. In some embodiments, the nature and availability of reactivefunctions on the separated solid lignin contribute to efficiency ofcompounding, e.g. with other polymers. In some embodiments, atemperature of the hot liquid influences the molecular weight of theseparated solid lignin.

The lignin composition of the invention can be identified by one or moreof the characteristics describing the atomic composition of thematerial. The weight percent of the lignin composition derived from eachelement can be measured by elemental analysis, for instance the percentof carbon, hydrogen, nitrogen, oxygen, sulfur can be measured. Forinstance, some elemental analysis data are presented in example 7. Thelignin of the invention can have up to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6,0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0% sulfur weight/weight. Insome embodiments, the lignin has less than 0.2% sulfur weight/weight. Insome embodiments, the lignin has less than 0.3, 0.2, 0.1 times theamount of sulfur found in Kraft softwood lignin. In some embodiments,the lignin has up to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0,1.5, 2.0, 3.0, 4.0, 5.0% nitrogen weight/weight. In some embodiments,the lignin has up to 0.5% nitrogen weight/weight. In some embodiments,the lignin has at least 35, 40, 45, 48, 49, 50, 55, 60, 62, 65, 67, 70%carbon weight/weight. In some embodiments, the lignin has between 48 and75% carbon weight/weight. In some embodiments, the lignin has at least1.1, 1.2, 1.3, 1.4 times the carbon weight/weight that Kraft softwoodlignin has. In some embodiments, the lignin has up to 4.0, 4.5, 5.0,5.5, 6.0, 6.5, 7.0, 7.5, 8.0% hydrogen weight/weight. In someembodiments, the lignin has between 5.0 and 7.5% hydrogen weight/weight.In some embodiments, the lignin has at least 1.1, 1.2, 1.3, 1.4 timesthe hydrogen weight/weight that Kraft softwood lignin has. In someembodiments, the lignin has up to 23, 24, 25, 26, 27, 28, 29, 30% oxygenweight/weight. In some embodiments, the lignin has less oxygenweight/weight than Kraft lignin does. The ratio of oxygen to carboncontent weight/weight (O/C) can be a measure of the oxidation of thelignin. The ratio of oxygen to carbon content weight/weight for thelignin of the invention can be up to 0.5, 0.45, 0.4, 0.39, 0.38, 0.37,0.36, 0.35, 0.34, 0.33, 0.32, 0.31, 0.3, 0.29, 0.28, 0.27, 0.26, 0.25,0.24, 0.22, or 0.2, for instance. In some embodiments, the lignin has aratio of oxygen to carbon content weight/weight (O/C) of less than 0.40.The lignin of the present invention can be less oxidized than Kraftsoftwood lignin. In some embodiments, the lignin can have an O/C weightratio less than that of Kraft softwood lignin. In some embodiments, thelignin can have an O/C weight ratio that is less than 0.9, 0.8, 0.7times the O/C ratio of Kraft softwood lignin. The empiric monomerformula can be calculated for a given lignin sample based on theelemental analysis. The resulting empiric formula can be of the formC_(a)H_(b)O_(c), wherein a, b, and c are numbers corresponding to therelative stoichiometry of the carbon, hydrogen, and oxygen atoms,respectively. In some embodiments, when a is set to 9, b is less than13, 12.5, 12, 11.5, 11, 10.5, 10. In some embodiments, when a is set to9, b is less than 12. In some embodiments, when a is set to 9 b isbetween 8.0 and 11.0. In some embodiments, when a is set to 9, c is lessthan 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.5. In someembodiments, when a is set to 9, c is less than 3.5. In someembodiments, when a is set to 9, c is between 2.0 and 3.5. In someembodiments, when a is set to 9, b is less than 12 and c is less than3.5. In some embodiments, when a is set to 9 b is between 8.0 and 11.0,and c is between 2.0 and 3.5.

Some chemical functional groups and their amounts in a lignincomposition can be measured by quantitative phosphorus nuclear magneticresonance (³¹P NMR) spectroscopy. For instance, a method of treating thelignin, parameters of the NMR experiments, and some of these data for avariety of lignin compositions are disclosed herein (example 8). In someembodiments, the lignin comprises up to 2 mmol aliphatic hydroxyl groupper gram lignin. In some embodiments, the lignin comprises up to 0.3,0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.5, 3.0, 3.5, 4.0 mmol aliphatic hydroxylgroup per gram lignin. In some embodiments, the lignin comprises feweraliphatic hydroxyl groups per gram lignin than Kraft softwood lignincomprises. In some embodiments, the lignin comprises between 0.2 and 2.0aliphatic hydroxyl groups (mmol/g lignin). In some embodiments, thelignin comprises at least 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 mmolphenolic hydroxyl per gram lignin. In some embodiments, the lignincomprises at least 3.0 phenolic hydroxyl group (mmol/g lignin). In someembodiments, the lignin comprises less than 0.5, 0.45, 0.40, 0.39, 0.38,0.37, 0.35, 0.30, 0.25, 0.20, 0.15, 0.1 carboxylic OH groups (mmol/glignin). In some embodiments, the lignin comprises less than 0.40mmole/g lignin carboxylic OH group. In some embodiments, the lignincomprises up to 2 mmol aliphatic hydroxyl group, at least 2.5 mmolphenolic hydroxyl groups, and less than 0.40 mmol carboxylic OH groupsper gram lignin.

Some chemical functional groups and their amounts in a lignincomposition can be measure by quantitative carbon nuclear magneticresonance (¹³C NMR) spectroscopy. For instance, the parameters of theNMR experiments, and data for a variety of lignin compositions isdisclosed herein (example 9). In some embodiments, the lignin has adegree of condensation less than 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5,0.4. In some embodiments, the lignin of the invention has a degree ofcondensation of less than 0.9. In some embodiments, the lignin of theinvention has a lower degree of condensation than that of ligninproduced through Organosolv process or Kraft milling. In someembodiments, the ratio of methoxyl groups per aryl group is at least0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3. In some embodiments, the methoxylcontent per aryl group is at least 0.8. In some embodiments, the ratioof aliphatic linkages (β-O-4′) per aryl groups is less than 0.3, 0.29,0.28, 0.27, 0.25, 0.2. In some embodiments, the ratio of aromatic C—Obonds per aryl group is less than 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6,1.5, 1.4. In some embodiments, the ratio of aromatic C—C linkages peraryl group is over 1.9, 2.0, 2.1, 2.2, 2.3. In some embodiments, theratio of aromatic C—H linkages per aryl group is between 1.5 and 2.2. Insome embodiments, the ratio of aromatic C—H linkages per aryl group isbetween 1.5 and 2.0. In some embodiments, the ratio of aromatic C—Hlinkages per aryl group is less than 2.0.

The composition of a lignin composition can be examined by inductivelycouple plasma analysis (ICP) to ascertain the concentration of traceelements. Additionally, the content of ash and carbohydrate can bedetermined by previously disclosed methods (National Renewable EnergyLaboratory (NREL) method TP-510-42622 and NREL method TP-510-42618,respectively). For instance, the experimental details and data for avariety of samples are disclosed herein (example 10). In someembodiments, the lignin of the invention comprises less than 1500, 1000,900, 800, 700, 691, 661, 650, 600, 500, 400, 200, 100 ppm sulfur. Insome embodiments, the lignin of the invention comprises less than 1000,500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5 ppm calcium. Insome embodiments, the lignin of the invention comprises less than 1500,1000, 900, 800, 700, 691, 661, 650, 600, 500, 400, 200, 100 ppm iron. Insome embodiments, the lignin of the invention comprises less than 1000,500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5 ppm potassium.In some embodiments, the lignin of the invention comprises less than1000, 500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5 ppmmagnesium. In some embodiments, the lignin of the invention comprisesless than 1000, 500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5ppm sodium. In some embodiments, the lignin of the invention comprisesless than 1000, 500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5ppm sulfur, calcium, iron, potassium, magnesium, and sodium. In someembodiments, the lignin of the invention comprises less than 5, 4, 3, 2,1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1% ash content. In someembodiments, the lignin comprises less than 0.1% ash. In someembodiments, the lignin comprises less than 1.0% ash. In someembodiments, the lignin comprises less than 5, 4, 3, 2, 1.0, 0.9, 0.8,0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1% carbohydrate content. In someembodiments, the trace carbohydrate content is comprised of 100, 99, 98,99, 95, 90, 85, 80, 70, 60, 50, 40, 30, 20, 10% glucose. In someembodiments, the carbohydrate content is less than 1% of the lignincontent weight/weight, and the carbohydrates are comprised of over 90%glucose. In some embodiments, the lignin of the invention comprises lessthan 1000, 500, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5 ppmsulfur, calcium, iron, potassium, magnesium, and sodium, and comprisesless than 1% ash and less than 1% carbohydrate.

The solubility of lignin in a variety of simple solvents at roomtemperature can be measured. For instance, the method and data aredisclosed herein (example 11). In some embodiments, the high puritylignin of the invention is insoluble in toluene and methylethylketone.In some embodiments, the lignin of the invention is soluble at greaterthan 1000, 500, 300, 200, 150, 120, 100, 50, 10, 1 g lignin per liter ofsolvent in DMSO. In some embodiments, the lignin of the invention issoluble at greater than 1000, 500, 300, 200, 150, 120, 100, 50, 10, 1 glignin per liter of solvent in THF. In some embodiments, the lignin ofthe invention is soluble at greater than 1000, 500, 300, 200, 150, 120,100, 50, 10, 1 g lignin per liter of solvent in a 0.1 N aqueous NaOHsolution. In some embodiments, the lignin has a solubility greater than120 g/L DMSO, >40 g/L THF, and >10 g/L 0.1 N NaOH. In some embodiments,the lignin has a solubility greater than 100 g/L DMSO, >35 g/L THF,and >8 g/L 0.1 N NaOH.

Lignin compositions can be characterized by the changes in physical andchemical properties as function of increasing temperature as measured byThermal Gravimetric Analysis (TGA). For instance, the TGA profiles oflignin samples are disclosed herein (example 12). In some embodiments,the lignin of the invention can have a moisture content of less than 15,14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.2,0.1% weight/weight. In some embodiments, the solid lignin can have lessthan 1% moisture content. In some embodiments, the lignin of theinvention reach 5% degradation at 200, 210, 220, 230, 240, 250, 260,270, 280, 290, 300° C. In some embodiments, the lignin of the inventionreach 10% degradation at 200, 210, 220, 230, 240, 250, 260, 270, 280,290, 300, 310, 320, 330, 340, 350, 360, 370, 380° C. In someembodiments, the lignin reaches 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20%degradation at 250° C. The char can be between 30 and 40% for example.

Lignin compositions can be characterized by differential scanningcalorimetry (DSC). For example, DSC was used to find the glass-liquidtransition, or glass transition, (Tg) of lignin of the invention anddisclosed herein (example 12, table 7b). DSC can be performed accordingto DIN 53765: wherein the sample is first dried by a pre-heat cycle; 2consecutive heat cycles are measured. Typically in the first cycleannealing processes can take place that affect the polymer structure,while in the second cycle the major transition Tg is ascribed to theglass transition of the polymer. The Tg value of the second cycle can beelevated by 4 to 30° C. In some embodiments, the lignin of the inventionis characterized by a glass transition elevation between first andsecond heat cycle according to DIN 53765 of more than 8, 9, 10, 11, 12,13, 14, 15, 16, 17, 18, 19, 20° C. In some embodiments, the lignin ofthe invention is characterized by a glass transition elevation betweenfirst and second heat cycle according to DIN 53765 of less than 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 32, 34°C. The term DIN and FINAT respectively refer to standardized testmethods for the determination of specific properties and which arewell-recognized and well-documented. In particular, DIN 53765 refers toDIN test method number 53765 for the testing of plastics and elastomers,especially thermal analysis by the DSC method (see U.S. Pat. No.5,595,810).

In some embodiments, the lignin of the invention is characterized by aglass transition elevation between first and second heat cycle accordingto DIN 53765 in the range of 10 to 30° C. In some embodiments, thelignin of the invention is characterized by a glass transition elevationbetween first and second heat cycle according to DIN 53765 in the rangeof 13 to 20° C.

In some embodiments, the lignin composition of the invention ischaracterized by at least one, two, three, four, five, six, seven,eight, nine, ten, eleven, twelve, or thirteen characteristic(s) selectedfrom the group consisting of: (i) lignin aliphatic hydroxyl group in anamount up to 2 mmole/g; (ii) at least 2.5 mmole/g lignin phenolichydroxyl group; (iii) less than 0.40 mmole/g lignin carboxylic hydroxylgroup; (iv) sulfur in an amount up to 1% weight/weight; (v) nitrogen inan amount up to 0.5% weight/weight; (vi) 5% degradation temperaturehigher than 220° C.; (vii) 10% degradation temperature higher than 260°C.; (viii) less than 1% ash weight/weight; (ix) a formula of CaHbOc;wherein a is 9, b is less than 12 and c is less than 3.5; (x) a degreeof condensation of less than 0.9; (xi) a methoxyl content of at least0.8; (xii) an O/C weight ratio of less than 0.4; and (xiii) a glasstransition elevation between first and second heat cycle according toDIN 53765 in the range of 10 to 30° C. In some embodiments, the lignincomposition is further characterized by one, two, three, four, five orsix, seven, eight, nine, or ten of additional characteristic(s) selectedfrom the group consisting of: (i) less than 1% carbohydrateweight/weight; (ii) solubility in DMSO is >100 g/L; (iii) solubility inTHF is >35 g/L; (iv) solubility in 0.1 N NaOH aqueous solution is >8g/L; (v) less than 1% water by weight; (vi) less than 1% volatilecomponents by weight; (vii) a sulfur concentration of less than 0.1%weight/weight; (viii) soluble sugar content of less than 1% byweight/weight; (ix) a phosphorus concentration of less than 100 PPM; and(x) less than 0.1 times the amount of volatile sulfur compounds found inKraft lignin.

The lignin compositions can be prepared from a substrate comprisingwood. In some embodiments, the lignin is derived from soft wood. In someembodiments, the lignin is derived from soft wood. In some embodiments,the lignin is derived from bagasse. The lignin can be a solid. In someembodiments, the lignin can be dissolved at least partially in anorganic solvent, such as an alcohol, a ketone, an aldehyde, an alkane,an organic acid and a furan of 6 carbons or less, for example. In someembodiments, lignin solution in methyl ethyl ketone is obtained by notremoving the solvent after the purification process. The lignincomposition can further comprise up to 20, 15, 10, 5, 4, 3, 2, 1, 0.50.4, 0.3, 0.2, or 0.1% cellulose weight/weight. Alternatively oradditionally, the composition can comprise less than 3, 2, 1.5, 1.0,0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.08, 0.05, 0.03, 0.01, or0.005% ash weight/weight.

The lignin composition 1760-P1 can further comprise marker molecules.The marker molecules can be a small percentage of the total weight ofthe lignin composition. Marker molecules can be detected by gaschromatography mass spec (GCMS) as disclosed herein (examples 17-19),for example. In some embodiments, the lignin of the invention orproducts made from the lignin can be characterized by comprising one ormore molecules selected from the group consisting of furfural andhydroxy-methyl furfural, 2,3,5 trimethyl furan, products of theircondensation, color compounds, acetic acid, p-hydroxyphenoxyacetic acid,4-hydroxy-3,5,-dimethoxyphenyl) acetic acid, methylethyl ketone,Methylpropenyl ketone, 3-(2-furyl)-3-penten-2-one,3-methyl-2-penten-4-one, 3,4-dimethyl-4-hexene-one,5-ethyl-5-hexene-3-one, 5-methyl-4-heptene-3-one, o-hydroxyanisole,3-ethyl-4-methyl-3-penten-2-one, 3,4,4-trimethyl-2-cyclohexene-1-one,2′-hydroxy-4′,5′-dimethylacetophenone,1-(4-hydroxy-3-methoxyphenyl)propane methanol, galacturonic acid,dihydroabietic acid, glycerol, fatty acids and resin acids. In someembodiments, the lignin or products derived from the lignin comprisemarker molecules derived from acetic acid or methylethyl ketone. In someembodiments, the lignin of the invention or products made from thelignin comprise one or more molecules selected from the group consistingof methylethyl ketone, 3,4-dimethyl-3-hexen-2-one,5-methyl-4-hepten-3-one, 5-ethyl-5hexen-3-one, 5-methyl-4-hepten-3-one,3-hydroxymethyl-2-butanone, 3,4-dimethyl-4-hexen-2one,5-ethyl-5-hexen-3one, and 5-methyl-5-hepten-3-one.

In some embodiments, the lignin composition described herein is producedby the process or methods described herein. The lignin compositiondescribed herein can be the product of the process of producing highpurity lignin from a biomass, comprising: (i) removing hemicellulosesugars from the biomass thereby obtaining a lignin-containing remainder;wherein the lignin-containing remainder comprises lignin and cellulose;(ii) contacting the lignin-containing remainder with a lignin extractionsolution to produce a lignin extract and a cellulosic remainder; whereinthe lignin extraction solution comprises a limited-solubility solvent,an organic acid, and water, wherein the limited-solubility solvent andwater form an organic phase and an aqueous phase; and (iii) separatingthe lignin extract from the cellulosic remainder; wherein the ligninextract comprises lignin dissolved in the limited-solubility solvent. Insome embodiments, the lignin of the invention is produced by the processfurther comprising one, two, three, four, or five additional step(s):(iv) contacting the lignin extract with a strong acid cation exchangerto remove residual cations thereby obtaining a purified lignin extract(v) optionally distilling or flash evaporating the lignin extractthereby removing the bulk of the limited-solubility solvent from thelignin extract to obtain solid lignin; (vi) heating the solid ligninthereby removing trace limited-solubility solvent or water from thesolid lignin; (vii) applying a vacuum to the solid lignin therebyremoving trace limited-solubility solvent or water from the solidlignin; and (viii) optionally dissolving the solid lignin with anorganic solvent to form a resulting solution and separating theresulting solution from insoluble remainder, as described herein. Insome of the embodiments, the lignin composition of the invention isproduced by the method or process described herein and the compositionis characterized by at least one of the following characteristics: (i)lignin aliphatic hydroxyl group in an amount up to 2 mmole/g; (ii) atleast 2.5 mmole/g lignin phenolic hydroxyl group; (iii) less than 0.40mmole/g lignin carboxylic OH group; (iv) sulfur in an amount up to 1%weight/weight; (v) nitrogen in an amount up to 0.5% weight/weight; (vi)5% degradation temperature higher than 220° C.; (vii) 10% degradationtemperature higher than 260° C.; (viii) less than 1% ash weight/weight;(ix) a formula of C_(a)H_(b)O_(c); wherein a is 9, b is less than 12 andc is less than 3.5; (x) a degree of condensation of less than 0.9; (xi)a methoxyl content of at least 0.8; (xii) an O/C weight ratio of lessthan 0.4; (xiii) a glass transition elevation between first and secondheat cycle according to DIN 53765 in the range of 10 to 30° C.; (xiv)less than 1% carbohydrate weight/weight; (xv) solubility in DMSO is >100g/L; (xvi) solubility in THF is >35 g/L; (xvii) solubility in 0.1 N NaOHaqueous solution is >8 g/L; (xviii) less than 1% water by weight; and(xix) less than 1% volatile components by weight. In some embodiments,the lignin composition of the invention is produced by the processdescribed herein and the composition is characterized by at least 5 ofthe above characteristics. In some embodiments, the composition isfurther characterized by 10 of the above characteristics.

V. Carbon Fibers and Lignin Conversion Products

Exemplary Spinning Processes:

In some embodiments, purified lignin dissolved in limited solubilitysolvent is concentrated by evaporating part of the solvent, to obtain ahigh viscosity composition; this high viscosity composition is span in aspinnerate to form a fiber, the fiber is contacted with an anti solventto remove the solvent and stabilize the fiber. These processes can beadapted to produce lignin fibers by wet spinning by adjusting variousparameters such as, for example, absolute and/or relative temperaturesof the two liquids and/or the concentration of lignin dissolved in thelimited-solubility solvent. In some embodiments, the concentration oflignin dissolved in the limited-solubility solvent contributes toviscosity of the lignin/solvent solution. In some exemplary embodimentsof the invention, there is provided a spinning method including, (a)providing a composition as described herein; (b) contacting thecomposition with an anti-solvent so that the lignin begins to solidify;(c) spinning the lignin to produce fibers. In some embodiments, themethod includes removing the antisolvent from the fibers.

In some embodiment, soluble lignin may be mixed with a synthetic polymerprior to wet spinning, to produce a composite fiber. Such syntheticpolymers may include but not limited to poly acrilonitrile, poly olefin.

In some exemplary embodiments of the invention, there is provided aspinning method including: (a) providing a solid lignin composition asdescribed above; (b) melting lignin in the composition; and (c) spinningand cooling the lignin to produce fibers. In some embodiments, themelting is conducted in the presence of plasticizers. In some exemplaryembodiments of the invention, there is provided a spinning methodincluding: (a) providing a composition as described above; and (b)spinning the lignin to produce fibers. In some embodiments, one or moreof the spinning methods described above includes stabilizing andcarbonizing the fibers to produce carbon fibers. In some exemplaryembodiments of the invention, a lignin fiber and/or carbon fiberproduced by a method as described above is used to produce a product.

Alternatively or additionally, some embodiments of the invention relateto products (or components of products) including and/or produced from afiber as described above (e.g. fabrics, sports equipment, automobiles,airplanes, boats, musical instruments and loudspeakers). Alternativelyor additionally, some embodiments of the invention relate to aninsulation material including a fiber as described above. Alternativelyor additionally, some embodiments of the invention relate to a compositematerial including a polymer including one or more materials selectedfrom the group consisting of epoxy, polyester, vinyl ester and nylonreinforced with fibers as described above. In some exemplary embodimentsof the invention, there is provided lignin 1760-P1, and characterized asdescribed herein.

Exemplary Modifying Reagents:

In some embodiments, lignin dissolved in limited-solubility solvent iscontacted with a modifying reagent. Optionally, a second liquid is themodifying reagent. In some embodiments, upon contact with the hotliquid, lignin reacts with and/or is coated by the modifying reagent.

Exemplary Coating Processes:

Some exemplary embodiments in which distillation is accomplished bycontacting the lignin dissolved in limited-solubility solvent with a hotsolid surface result in coating of the solid surface with a ligninlayer. According to some embodiments such coating serves to encapsulatethe solid surface. Encapsulation of this type is useful, for example, inslow-release fertilizer formulation and/or in provision of a moisturebarrier. In some embodiments, the solid to be coated is provided asfibers. The resultant coated fibers are useful, for example, in themanufacture of composite materials. In some embodiments, the lignin isdissolved in a volatile solvent (e.g. MEK). Use of a volatilelimited-solubility solvent contributes to a capacity for coating ofthermally sensitive solids. In some embodiments, a plasticizer is addedto the lignin dissolved in limited-solubility solvent. Optionally, theplasticizer contributes to an improvement in the resultant coating.

Polymer Organization:

In some embodiments, the lignin dissolved in limited-solubility solventis co-sprayed with a second polymer that has a linear arrangement tocause formation of rod like assemblies of lignin molecules. Resultantco-polymer arrangements with a high aspect ratio are useful instructural applications (e.g. carbon fibers). In some exemplaryembodiments of the invention, the lignin composition is mixed with asynthetic polymeric material. According to various exemplary embodimentsof the invention the synthetic polymeric material includespolyacrylonitrile (PAN) and/or polypropylene and/or ABS and/or mylon. Insome exemplary embodiments of the invention, a ratio of lignin:syntheticpolymer (e.g. PAN) is ≧1:10; ≧1.5:10; ≧2:10; ≧2.5:10; ≧3:10 or; ≧3.5:10.Alternatively or additionally, in some embodiments a ratio oflignin:synthetic polymer (e.g. PAN) is ≦10:1; ≦9:1; ≦9:1; ≦5:1; ≦6:1;≦50:1.

In some exemplary embodiments of the invention, methods end withproduction of lignin fibers as described above. In other exemplaryembodiments of the invention, methods transform the lignin fibers tocarbon fibers by carbonizing the lignin fibers. In some exemplaryembodiments of the invention, carbonizing the lignin fibers is conductedconcurrently on lignin and synthetic polymeric material (e.g.polyacrylonitrile). These embodiments produce carbon fibers whichinclude a mixture of carbonized lignin and carbonized syntheticpolymeric material.

According to various exemplary embodiments of the invention, the aspectratio of a transverse cross-sectional dimension to length of theobserved tubules is less than 0.1, less than 0.05, less than 0.025, lessthan 0.02, or less than 0.01. In some exemplary embodiments of theinvention, lignin particles with a greatest dimension less than 100 μmhave a length: width aspect ratio of ≧1.5; ≧2.5; ≧3.5 or ≧5.0. In someexemplary embodiments of the invention, there is provided a ligninparticle characterized by lengthwise tubules with a transversecross-sectional dimension of at least 5 microns. In some embodiments,the transverse cross-sectional dimension is less than 20 microns.Alternatively or additionally, in some embodiments the tubules arecharacterized by an aspect ratio of transverse cross-sectional dimensionto length less than 0.1. Alternatively or additionally, in someembodiments the aspect ratio is less than 0.025. Alternatively oradditionally, in some embodiments at least 0.1% of particles in thepopulation are particles as described herein.

Further Lignin Products

In some exemplary embodiments of the invention, there is provided aprocessed product produced by a method as described above. In someexemplary embodiments of the invention, there is provided a methodincluding: providing a processed product as described above; andsubjecting the processed product to an industrial process to produce adownstream product.

Optionally, the downstream product is selected from the group consistingof a hygienic pad, a diaper and a wound dressing, sports equipment, astructural component, a paint and a dye. In some exemplary embodimentsof the invention, there is provided a downstream product produced by amethod as described above.

In some exemplary embodiments of the invention, there is provided amethod including providing a processed product as described above; andusing the processed product as an ingredient or component in adownstream product. Optionally, the downstream product is selected fromthe group consisting of a liquid fuel, a paint, a dye, a glue and aplastic. In some exemplary embodiments of the invention, there isprovided a downstream product produced by a method as described above.

In some exemplary embodiments of the invention, a lignin composition asdescribed herein is provided as part of a product comprising otheringredients. Alternatively or additionally, in some embodiments, alignin composition as described herein is used in preparation of anothermaterial or product. Examples of such materials/products include, butare not limited to, carbon fibers, protective coatings, lignosulfonates,bio-oils, carboxylic and fatty acids, dicarboxylic acids,hydroxyl-carboxylic, hydroxyl di-carboxylic acids and hydroxyl-fattyacids, methylglyoxal, mono-, di- or poly-alcohols, alkanes, alkenes,aromatics, aldehydes, ketones, esters, biopolymers, proteins, peptides,amino acids, vitamins, antibiotics, paraxylene, pharmaceuticals,dispersants, emulsifiers, complexants, flocculants, agglomerants,pelletizing additives, resins, antioxidants, liquid fuels, aromaticchemicals, vanillin, adhesives, binders, absorbents, toxin binders,foams, films, rubbers, elastomers, sequestrants, solid fuels, expandersa liquid fuels, paints, dyes, glues, plastics, wet spun fibers, meltspun fibers, flame retardants, activated carbon, activated carbonfibers, absorbent materials (e.g. in hygienic pads, diapers or wounddressings), phenol resins, phenols, terephthalates, epoxies, BTX(Benzene/Toluene/Xylene), polyols and polyolefins, each of whichrepresents an additional exemplary embodiment of the invention. In someembodiments, the product is selected from the group consisting of:carbon fibers, protective coatings, lignosulfonates, pharmaceuticals,dispersants, emulsifiers, complexants, flocculants, agglomerants,pelletizing additives, resins, adhesives, binders, absorbents, toxinbinders, films, rubbers, elastomers, sequestrants, solid fuels, paints,dyes, plastics, wet spun fibers, melt spun fibers and flame retardants.In some embodiments, the product is selected from the group consistingof: a non woven fabric, a woven fabric, insulation material, sportsequipment, automotive parts, airplane or helicopter parts, boat hulls orportions thereof and loudspeakers. In some embodiments, the product is acomposite material comprising a polymer and one or more materialsselected from the group consisting of epoxy resin, polyester, polyvinylester and nylon, wherein the polymer is reinforced with fiberscharacterized herein.

Lignin Applications

The high purity lignin composition according to embodiments disclosedherein has a low ash content, a low sulfur and/or phosphorousconcentration. Such a high purity lignin composition is particularlysuitable for use in catalytic reactions by contributing to a reductionin catalyst fouling and/or poisoning. A lignin composition having a lowsulfur content is especially desired for use as fuel additives, forexample in gasoline or diesel fuel.

Some other potential applications for high purity lignin includecarbon-fiber production, asphalt production, and as a component inbiopolymers. These uses include, for example, oil well drillingadditives, concrete additives, dyestuffs dispersants, agriculturechemicals, animal feeds, industrial binders, specialty polymers forpaper industry, precious metal recovery aids, wood preservation,sulfur-free lignin products, automotive brakes, wood panel products,bio-dispersants, polyurethane foams, epoxy resins, printed circuitboards, emulsifiers, sequestrants, water treatment formulations,strength additive for wallboard, adhesives, raw materials for vanillin,xylitol, and as a source for paracoumaryl, coniferyl, sinapyl alcohol.In some embodiments, the properties of an asphalt composition can beimproved by using the lignin of the invention. The asphalt can beimproved, for instance, by compounding the asphalt mixture with a least2% wt/wt solid lignin made using the lignin of the invention. Theimproved properties of the asphalt can be selected from one or two orthree of the following characteristics: (i) stability against oxidation;(ii) stability against UV radiation; (iii) having a renewable carboncomponent.

Exemplary Lignin Conversion Method

Referring again to FIG. 7, in some embodiments, method 200 includesconverting 210 at least a portion of lignin in lignin stream 208 to aconversion product 212. In some embodiments, converting 210 employsdepolymerization, oxidation, reduction, precipitation (by neutralizationof the solution and/or by solvent removal), pyrolysis, hydrogenolysis,gasification, or sulfonation. In some embodiments, conversion 210 isoptionally conducted on lignin while in solution, or afterprecipitation. In some embodiments, converting 210 includes treatinglignin with hydrogen. In some embodiments, converting 210 includesproducing hydrogen from lignin.

In some embodiments, conversion product 212 includes at least one itemselected from the group consisting of bio-oil, carboxylic and fattyacids, dicarboxylic acids, hydroxylcarboxylic, hydroxyldicarboxylicacids and hydroxyl-fatty acids, methylglyoxal, mono-, di- orpoly-alcohols, alkanes, alkenes, aromatics, aldehydes, ketones, esters,phenols, toluenes, and xylenes. In some embodiments, the conversionproduct includes a fuel or a fuel ingredient. Optionally, the conversionproduct includes para-xylene.

In some embodiments, converting 210 includes aqueous phase reforming. Insome embodiments, converting 210 includes at least one bioformingreaction. Exemplary bioforming reaction types include catalytichydrotreating and catalytic condensation, zeolite (e.g. ZSM-5) acidcondensation, base catalyzed condensation, hydrogenation, dehydration,alkene oligomerization and alkylation (alkene saturation). In someembodiments, the converting occurs in at least two stages (e.g. 210 and220) which produce conversion products 212 and 222 respectively.Optionally, a first stage (210) includes aqueous phase reforming. Insome embodiments, second stage 220 includes at least one of catalytichydrotreating and catalytic condensation.

Optionally, method 200 is characterized by a hydrogen consumption ofless than 0.07 ton per ton of product 212 and/or 222.

Exemplary Lignin Products

The present invention also provides a consumer product, a precursor of aconsumer product or an ingredient of a consumer product produced from alignin stream 208. In some embodiments, the consumer product ischaracterized by an ash content of less than 0.5% wt and/or by acarbohydrates content of less than 0.5% wt and/or by a sulfur content ofless than 0.1% wt and/or by an extractives content of less than 0.5% wt.In some embodiments, the consumer product produced from lignin stream208 includes one or more of bio-oil, carboxylic and fatty acids,dicarboxylic acids, hydroxylcarboxylic, hydroxyldicarboxylic acids andhydroxyl-fatty acids, methylglyoxal, mono-, di- or poly-alcohols,alkanes, alkenes, aromatics, aldehydes, ketones, esters, biopolymers,proteins, peptides, amino acids, vitamins, antibiotics, andpharmaceuticals. In some embodiments, the consumer product includes oneor more of dispersants, emulsifiers, complexants, flocculants,agglomerants, pelletizing additives, resins, carbon fibers, activecarbon, antioxidants, liquid fuel, aromatic chemicals, vanillin,adhesives, binders, absorbents, toxin binders, foams, coatings, films,rubbers and elastomers, sequestrants, fuels, and expanders. In someembodiments, the product is used in an area selected from the groupconsisting of food, feed, materials, agriculture, transportation andconstruction. Optionally, the consumer product has a ratio of carbon-14to carbon-12 of about 2.0×10⁻¹³ or greater.

Some embodiments relate to a consumer product containing an ingredientas described above and an ingredient produced from a raw material otherthan lignocellulosic material. In some embodiments, the ingredient andthe ingredient produced from a raw material other than lignocellulosicmaterial are essentially of the same chemical composition.

In some embodiments, the consumer product includes a marker molecule ata concentration of at least 100 ppb. In some embodiments, the markermolecule is selected from the group consisting of furfural andhydroxymethylfurfural, products of their condensation, color compounds,acetic acid, methanol, galacturonic acid, glycerol, fatty acids andresin acids.

In some embodiments, the product is selected from the group consistingof dispersants, emulsifiers, complexants, flocculants, agglomerants,pelletizing additives, resins, carbon fibers, active carbon,antioxidants, liquid fuel, aromatic chemicals, vanillin, adhesives,binders, absorbents, toxin binders, foams, coatings, films, rubbers andelastomers, sequestrants, fuels, and expanders.

VI. Method of Producing Cellulose Pulp Remainder from Direct LigninExtraction Method.

The direct lignin extraction method described in section IV solubilizeslignin from lignocellulosic biomass leaving behind an insoluble material(FIGS. 5, 1760->1760-P1). The material that is insoluble in theextraction solvent can be deemed the cellulosic remainder pulp. In someembodiments, the present invention is a method of producing cellulosefrom a biomass, comprising: (i) removing hemicellulose sugars from thebiomass thereby obtaining a lignocellulosic remainder; wherein thelignocellulosic remainder comprises lignin and cellulose; (ii)contacting the lignocellulosic remainder with a lignin extractionsolution to produce a lignin extract and a cellulosic remainder; whereinthe lignin extraction solution comprises a limited-solubility solvent,an organic acid, and water, wherein the limited-solubility solvent andwater form an organic phase and an aqueous phase; (iii) separating thelignin extract from the cellulosic remainder; wherein the lignin extractcomprises lignin dissolved in the limited-solubility solvent; and (iv)obtaining cellulosic remainder pulp.

Composition of Cellulosic Pulp Remainder

The cellulosic remainder pulp from the direct extraction oflignocellulosic can be characterized by the contents and properties ofthe composition. For instance, the remainder pulp is characterizedaccording to NREL method TP-510-42618 and the data are disclosed herein(pulp from bagasse: Example 14, pulp from eucalyptus and pine: Example15). Briefly, this test comprises hydrolysis of the cellulose andhemicellulose polymers in sulfuric acid; the dissolved sugars aredetermined, the amount of carbohydrates in the biomass are calculated,and lignin is determined as the remaining solids. In some embodiments,the cellulosic remainder pulp has a C6 sugars to solid ratio of morethan 45, 50, 55, 60, 65, 70, 75, 80, 83, 85, 90, 95, 99% weight/weight.In some embodiments, the cellulosic remainder pulp has a glucose tosolid ratio of 45, 50, 55, 60, 65, 70, 75, 80, 83, 85, 90, 95, 99%weight/weight. In some embodiments, the remainder pulp has a C5 sugarsto solid ratio of less than 10, 5, 4, 3, 2, 1% weight/weight. In someembodiments, the cellulosic remainder pulp has a total sugars to solidratio of more than 45, 50, 55, 60, 65, 70, 75, 80, 83, 85, 90, 95, 99%weight/weight. In some embodiments, the cellulosic remainder pulpcomprises less than 15, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3% ligninweight/weight. In some embodiments, the cellulosic remainder pulpcomprises less than 20, 15, 13, 10, 8, 7, 5, 4, 3, 2, 1% ashweight/weight. In some embodiments, the cellulosic remainder pulp ischaracterized by (i) C6 sugars to solid ratio of >70% weight/weight;(ii) glucose to solid ratio of >70% weight/weight; (iii) C5 sugars tosolid ratio of <5% weight/weight; or (iv) total sugars to solid ratioof >75% weight/weight. In some embodiments, the cellulosic remainderpulp is characterized by (i) C6 sugars to solid ratio of >70%weight/weight; (ii) glucose to solid ratio of >70% weight/weight; (iii)C5 sugars to solid ratio of <5% weight/weight; and (iv) total sugars tosolid ratio of >75% weight/weight.

The amount of inorganic impurities in a cellulosic remainder pulp samplecan be measured by inductively coupled plasma atomic emissionspectrometry (ICP-AES). For instance, the remainder pulp ischaracterized and the data are disclosed herein (from bagasse: Example14, from eucalyptus and pine: Example 15). In some embodiments, thecellulosic remainder comprises an amount of trace sulfur less than 1000,900, 800, 700, 600, 500, 400, 300, 200, 100 ppm. In some embodiments,the cellulosic remainder comprises an amount of trace calcium less than1000, 900, 800, 700, 600, 500, 400, 300, 200, 100 ppm. In someembodiments, the cellulosic remainder comprises an amount of trace ironless than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100 ppm. In someembodiments, the cellulosic remainder comprises an amount of tracepotassium less than 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100,50 ppm. In some embodiments, the cellulosic remainder comprises anamount of trace magnesium less than 500, 400, 300, 200, 100, 90, 80, 70,60, 50, 40, 30, 20, 10 ppm. In some embodiments, the cellulosicremainder comprises an amount of trace sodium less than 500, 400, 300,200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 ppm. In some embodiments,the cellulosic remainder comprises an amount of trace chromium less than500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10 ppm. In someembodiments the cellulosic remainder comprises less than 10 ppm of Mg,Mn, Na, Zn; and the amount of trace Cu, Fe, K, Al, Cr, is less than 200ppm.

The cellulosic remainder pulp from the direct extraction oflignocellulosic can be characterized according to the monograph ofmicrocrystalline cellulose in the Food Chemical Codex (FCC), 5^(th) Ed.(2004) published by The Food and Nutrition Board of The NationalAcademy, Institute of Medicine, Washington, by the solubility in avariety of solvents. Additionally, the cellulose composition can passthe microcrystalline cellulose identification tests A and B. Passing theidentification tests A and B can mean: A) a white opaque, bubble-freedispersion which does not form a supernatant liquid at the surface isobtained after 100 mL of a dispersion 45 g of cellulose in 255 mL wateris mixed for 5 minutes in a high-speed power blender (18,000 rpm) isleft standing in a 100-mL graduate for 3 hours, and B) 20 mL of thedispersion is mixed with a few drops of iodine TS and no purplish toblue or blue color is produced. For instance, the solubility of avariety of cellulosic remainder pulps are measured and disclosed herein(Example 16). In some embodiments, the cellulosic remainder has aconductivity of less than 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50,45, 40, 35, 30 μS/cm. In some embodiments, the cellulosic remainder hasa conductivity of more than 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25,20, 15, 10, 5 μS/cm. In some embodiments, the cellulosic remainder has aconductivity of between 10 and 70 μS/cm. In some embodiments, thecellulosic remainder contains less than 2, 1.5, 1.0, 0.8, 0.6, 0.4, 0.3,0.25, 0.24, 0.23, 0.22, 0.20, 0.19, 0.15, 0.1% water soluble substancesweight/weight. In some embodiments, the cellulosic remainder containsless than 0.25% water soluble substances weight/weight. In someembodiments, the cellulosic remainder comprises less than 50, 40, 30,20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5 mg water soluble substancesper 5 gram cellulosic remainder. In some embodiments, the cellulosicremainder comprises less than 15 mg water soluble substances per 5 gramcellulosic remainder. In some embodiments, the cellulosic remaindercomprises less than 50, 40, 30, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6,5, 4, 3, 2, 1 mg ether soluble substances per 10 gram cellulosicremainder. In some embodiments, the cellulosic remainder comprises lessthan 30 mg ether soluble substances per 10 gram cellulosic remainder. Insome embodiments, the cellulosic remainder has a pH less than 7, 6.8,6.5, 6.3, 6, 5, or 4 in water. In some embodiments, the cellulosicremainder has a pH between about 4 and about 7 in water. In someembodiments, the cellulosic remainder has a conductivity of between 10and 70 μS/cm; contains less than 0.25% water soluble substancesweight/weight; comprises less than 15 mg water soluble substances per 5gram cellulosic remainder; comprises less than 30 mg ether solublesubstances per 10 gram cellulosic remainder; and has a pH between about4 and about 7 in water. In some embodiments, the cellulosic remainderhas similar properties to Avicell PH-200 cellulose and other Avicellgrades.

The insoluble remainder pulp can be characterized by one or more two ormore, three or more, or four or more of the following characteristics:(i) cellulose to solid ratio of >85% weight/weight; (ii) crystallinecellulose to solid ratio of >50% weight/weight; (iii) lignin to solidratio of <10% weight/weight; and (iv) hemicellulose carbohydrate tosolid ratio of <4% weight/weight. In some embodiments, the pulp isfurther characterized by being comprised of cellulose at more than 90%weight/weight. In some embodiments, the pulp is further characterized bycomprising one or more, two or more, three or more, four or more, fiveor more, or six or more of the following characteristics: (i) C6 sugarsto solid ratio of >70% weight/weight; (ii) glucose to solid ratioof >70% weight/weight; (iii) C5 sugars to solid ratio of <5%weight/weight; (iv) total sugars to solid ratio of >75% weight/weight;(v) trace Mg, Mn, Na, Zn <10 ppm; and (vi) trace Cu, Fe, K, Al, Cr, <200ppm. In some embodiments, the pulp is further characterized by one ormore, two or more, three or more, four or more, five or more, or six ormore, seven or more, eight or more, nine or more, ten or more, eleven ormore, or twelve or more of the following characteristics: (i) a loss ofdrying from 2.0-5.0%; (ii) bulk density of 0.29-0.36 g/cc; (iii) passesidentification tests A and B; (iv) degree of polymerization is no morethan 350 units; (v) pH is 5.5-7.0; (vi) conductivity is not more than 75μS/cm; (vii) residue on ignition is not more than 0.05% weight/weight;(viii) water soluble substances are not more than 12.5 mg/5 g; (viii)ether soluble substances are not more than 5.0 mg/10 g; (ix) heavymetals are not more than 0.001% weight/weight; (x) soluble in coppertetramine hydroxide; (xi) particle size under 250 microns is not lessthan 10% weight/weight; and (xii) particle size under 150 microns is notless than 50% weight/weight. The cellulosic remainder can be furthercharacterized by comprising cellulose at more than 80, 85, 90, 92, 94,96, 98, 99%. The loss of drying can be % of material lost weight/weightwhen the sample is dried from a solid to dry solid. The sample can beheated for a period of time to dry. The sample can be heated to 200,190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50,40, 30° C. for the period of time to dry. The period of time the sampleis heated to dry the sample can be 100, 90, 80, 70, 60, 50, 48, 40, 30,24, 20, 16, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 hours.

In some embodiments, cellulose composition comprises one or more, two ormore, three or more, four or more of the following characteristics: (i)cellulose to solid ratio of >90% weight/weight; (ii) crystallinecellulose to solid ratio of >50% weight/weight; (iii) lignin to solidratio of <10% weight/weight; and (iv) hemicellulose carbohydrate tosolid ratio of <4% weight/weight. In some embodiments, the cellulosecompositions are characterized by a high cellulose to solid ratio, a lowlignin to solid ratio, and a low hemicellulose carbohydrate to solidratio. In some embodiments, the cellulose compositions are characterizedby a high crystalline cellulose to solid ratio. In some embodiments, thecellulose compositions are characterized by a high cellulose to solidratio, a low lignin to solid ratio, a high crystalline cellulose tosolid ratio and a low hemicellulose carbohydrate to solid ratio. In somecellulose compositions, cellulose to solid ratio is larger than 90%,92%, 94%, 96%, 98%, or 99% weight/weight. In some cellulosecompositions, crystalline cellulose to solid ratio is larger than 50%,60%, 70%, 80%, 90% weight/weight. In some cellulose compositions, ligninto solid ratio is less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%weight/weight. In some cellulose compositions, hemicellulosecarbohydrate to solid ratio is less than 4%, 3%, 2%, or 1%.

VII Conversion of Cellulosic Remainder Pulp

The cellulosic remainder pulp of the present invention can be convertedto a conversion product using a chemical or a biological process. Thechemical process can be catalysis, biochemical transformation, or athermochemical transformation. The conversion product can be a chemicalderivative of cellulose. The conversion product can be a value-addedproduct. The conversion product can be a renewable chemical or material,a nutrition supplement, or a bioenergy product. The conversion productcan comprise at least one member selected from the group consisting ofhalomethylfurfural, hydroxymethylfurfural, furfural, para-xylene, or anycombination thereof. The conversion product can be lactic acid, lysine,threonine, p-xylene, PHA, succinic acid, ethanol, jet fuel, diesel,xylitol, Bakers' yeast, butanol, feedstock for BTX, BTX, fermentablesugars, dimethyl furan, furan dicarboxylic acid (FDCA), adipic acid, orbuilding block chemicals, for example.

The conversion product can be used to produce a consumer product. Theconsumer product can be any product produced from cellulose. Theconsumer product can be a texturizer, an anti-caking agent, a fatsubstitute, an emulsifier, an extender, thin layer chromatographystationary phase, filler in a drug tablet, a bulking agent in foodproduction, plaque assay kit, or a surfactant, for example.

Exemplary Lignocellulosic Remainder Composition

Some embodiments relate to the remainder lignocellulosic 1700-P1composition prepared by a method as described hereinabove. Suchcomposition has less than 20%, less than 15%, less than 13%, less than10% weight/weight hemicelluloses carbohydrates on a dry matter basis. Insome embodiments, such composition is at least 40%, 50%, 60%weight/weight cellulose, and at least 20%, or at least 30% weight/weightlignin. In some embodiments, acid soluble lignin is less than 5%, lessthan 3% less than 2% weight/weight. In some embodiment the residualamount of calcium in 1700-P1 is less than 90%, less than 80%, less than70%, less than 60%, less than 50% weight/weight that of the nativelignocellulose matter. In some embodiment the residual amount ofmagnesium in 1700-P1 is less than 90%, less than 80%, than 70%, lessthan 60%, less than 50% weight/weight that of the native lignocellulosematter.

The change in composition of the remainder lignocellulosic 1700-P1compared to the native lignocellulose matter used to generate it throughtreatment 1700 is reflected in its properties: while nativelignocellulosic matter is hard to grind, the remainder 1700-P1 isbrittle and can be easily ground or milled by common industrialequipment to produce powders that can be pumped as solid suspension in aliquid or in a solid flow.

Exemplary Solid Cellulose Composition Characteristics

In some embodiments, solid cellulose composition 150 includes at least80%, 85%, 90%, 95%, or 98% cellulose on a dry matter basis. In someembodiments, the cellulose in solid cellulose composition 150 (FIG. 9)is at least 40%, 50%, 60%, 70% or 80% crystalline. In some embodiments,less than 50%, 40%, 30% or 20% of the cellulose in solid cellulosecomposition 150 (FIG. 9) is crystalline cellulose.

In some embodiments, solid cellulose composition 150 (FIG. 9) includesat least 85%, 90%, 95% or 98% of the cellulose in lignocellulosesubstrate 110. In some embodiments, solid cellulose composition 150includes less than 50%, less than 60%, less 70% or less than 80% of theash in lignocellulose substrate 110. In some embodiments, solidcellulose composition 150 includes less than 50%, less than 60%, less70% or less than 80% of the calcium ions in lignocellulose substrate110. In some embodiments, solid cellulose composition 150 includes lessthan 30% 20%, 10% or even less than 5% weight/weight of the lipophilicmaterials in lignocellulose substrate 110. In some embodiments, solidcellulose composition 150 includes in an amount up to 30% 20%, 10% or 5%weight/weight of the lignin in lignocellulose substrate 110. In someembodiments, solid cellulose composition 150 includes water-solublecarbohydrates at a concentration of less than 10% wt, 8% wt, 6% wt, 4%wt, 2% wt, or 1% wt. In some embodiments, solid cellulose composition150 includes acetic acid in an amount ≦50%, ≦40%, ≦30 or even ≦20%weight/weight of the acetate function in 110.

In some embodiments, lignocellulose substrate 110 includes pectin.Optionally, solid cellulose composition 150 includes less than 50%, 40%,30%, or 20% weight/weight of the pectin in substrate 110. In someembodiments, lignocellulose substrate 110 includes divalent cations.Optionally, solid cellulose composition 150 includes less than 50%, 40%,30%, or 20% weight/weight of divalent cations present in substrate 110.

In some embodiments, cellulose 1760-P2 (FIG. 10A) includes at least 80%,85%, 90%, 95%, or 98% cellulose weight/weight on a dry matter basis. Insome embodiments, the cellulose in solid cellulose composition 1760-P2is at least 40%, 50%, 60%, 70% or 80% crystalline weight/weight on a drysolid basis. In some embodiments, less than 50%, 40%, 30% or 20%weight/weight on a dry solid basis of the cellulose in solid cellulosecomposition 1760-P2 is crystalline cellulose.

In some embodiments, solid cellulose composition 1760-P2 includes atleast 85%, 90%, 95% or 98% of the cellulose in lignocellulose substrate1700-P1. In some embodiments, solid cellulose composition 1760-P2includes less than 50%, less than 60%, less 70% or less than 80% of theash in the native lignocellulose matter. In some embodiments, solidcellulose composition 1760-P2 includes less than 50%, less than 60%,less 70% or less than 80% of the calcium ions in native lignocellulosematter. In some embodiments, solid cellulose composition 1760-P2includes in an amount up to 30% 20%, 10% or 5% weight/weight of thelignin in native lignocellulose matter. In some embodiments, solidcellulose composition 1760-P2 includes hemicellulose carbohydrates at aconcentration of less than 10% wt, 8% wt, 6% wt, 4% wt, 2% wt, or 1% wt.In some embodiments, solid cellulose composition 1760-P2 includes aceticacid in an amount ≦50%, ≦40%, ≦30 or even ≦20% weight/weight of theacetate function in native lignocellulose matter.

In some embodiments, cellulose composition 1760-P2 includes pectin.Optionally, solid cellulose composition 1760-P2 includes less than 50%,40%, 30%, or 20% weight/weight of the pectin in native lignocellulosematter. In some embodiments, native lignocellulose matter includesdivalent cations. Optionally, solid cellulose composition 1760-P2includes less than 50%, 40%, 30%, or 20% weight/weight of divalentcations present in substrate 110.

The cellulose product 1760-P2 comprises less than 20%, less than 10%,9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% lignin and less than 5%, 4%, 3%, 2%, lessthan 1% hemicelluloses weight/weight on a dry solid basis. Saidcellulose product is separated from the acid solvent reaction mixture aswhite solid that is filtered or sedimented and washed with additionalamounts of MEK and or water to remove additional dissolved lignin orsugars, the solid is then dried.

This cellulose product may be fully hydrolyzed to high purity glucose asdisclosed in PCT/US2013/039585 (incorporated herein by reference for allpurposes). Alternatively, the cellulose product may be fully hydrolyzedto high purity glucose by chemical methods, including low temperatureHCl hydrolysis as disclosed in PCT/US2013/039585 (incorporated herein byreference for all purposes), or any other chemical hydrolysis includingbut not limited to hydrolysis with dilute acid at high temperature, acidcatalyzed hydrolysis in ionic liquid, solid state catalyzed hydrolysisutilizing sulfonated polymer or sulfonated activated carbon as catalyst.

In one method, hydrolysis is carried out in mild conditions thathydrolyze only the remaining amorphous cellulose, leaving thecrystalline cellulose as crystals. Mild hydrolysis can be conducted indilute solution of any of the acids HCl, H₂SO₄, HNO₃ and other acids, aswell as mixtures thereof. The resulting nano crystals can beprecipitated from the aqueous solution by changing the ionic strength ofthe solution, for example by dilution with water, or by adding anon-solvent to cause precipitation by centrifuge. Nano crystallinecellulose may have various applications as a component in bio-compositematerials, the crystalline cellulose serving as a nano-strengtheningcomponent in the composite.

In another embodiment, the cellulose product is used as feedstock for achemical conversion to produce furans. Such conversion may be done byheating it in the presence of a phenyl boronic acid and optionallymagnesium or calcium halide salt. The reaction is carried out in a polaraprotic solvent other than an ionic liquid, an ionic liquid. or amixture thereof, optionally with addition of small amounts of water.Alternatively, cellulose can be converted to furans in concentratedZnCl₂ solutions under microwave radiation. Such solution comprisinggreater than 50%, 60% 70% ZnCl₂ and cellulose is irradiated with MWradiation of 400-800 W for ca. 5 min to convert cellulose to a mixtureof furan isomers.

In another method, ionic liquids having a sulfonic acid functionality,e.g. 1-(4-sulfonic acid) butyl-3-methylimidazolium hydrogen sulfate(IL-1) are used to convert under mild conditions microcrystallinecellulose to furans. The reaction is co-catalyzed by metal ions selectedfrom Cr³⁺, Mn²⁺, Fe³⁺, Fe—, Co²⁺ as their chloride or sulfate salts. Theprocess may be further catalyzed by MW irradiation.

Alternatively, cellulose product 1760-P1 is converted to substitutedfurans (e.g., halomethylfurfural, hydroxymemylfurfural, and furfural) byacid-catalyzed conversion of biomass containing glycans (e.g.,cellulose) using a gaseous acid in a multiphase reactor. The process forproducing a substituted furan in a multiphase reactor consists of:feeding biomass and a gaseous acid into a multiphase reactor; and mixingthe biomass and the gaseous acid in the presence of a proton donor and asolvent to form a reaction mixture, under conditions suitable to producea substituted furan, in which the reaction mixture has less than 10% byweight of water. The gaseous acid is separated from the solid in agas-solid separator, and the gas is dried. The multi phase reactor maybe a fluidized bed reactor. Suitable Lewis acids may include, forexample, lithium chloride, sodium chloride, potassium chloride,magnesium chloride, calcium chloride, zinc chloride, aluminum chloride,boron chloride, or any combination thereof. In other embodiments, theproton donor has less than 10% by weight of water. Suitable solvent isselected from dichloromethane, ethylacetate, hexane, cyclohexane,benzene, toluene, diethyl ether, tetrahydrofuran, acetone, dimethylformamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol,isopropanol, n-propanol, n-butanol, chloroform, dichloroethane,trichloroethane, furfural, furfuryl alcohol, supercritical carbondioxide, and any combination thereof. In some embodiments, the solventis dry. In other embodiments, the solvent has less than 10% by weight ofwater.

Once these substituted furans are produced, they can serves asintermediates that can be converted into to furanic derivatives such asbiofuels, diesel additives, and plastics. In one embodiment, substitutedfuran, i.e. 2,5-dimethylfuran (DMF) is converted into para-xylene bycycloaddition of ethylene. Specifically, DMF and ethylene may be reactedin the presence of activated carbon to produce para-xylene.Alternatively, DMF and ethylene may be reacted in the presence of anacid, a desiccant, or an acid and a desiccant to produce a reactionmixture comprising para-xylene wherein less than 10% of the reaction is2,5-hexanedione. The method further includes oxidizing para-xylene toproduce terephthalic acid. The method further includes producing one ormore plastics or fuels from para-xylene.

EXAMPLES

It is understood that the examples and embodiments described herein arefor illustrative purposes only and are not intended to limit the scopeof the claimed invention. It is also understood that variousmodifications or changes in light the examples and embodiments describedherein will be suggested to persons skilled in the art and are to beincluded within the spirit and purview of this application and scope ofthe appended claims. All publications, patents, and patent applicationscited herein are hereby incorporated by reference in their entirety forall purposes.

Example 1—Small Scale Hemicellulose Sugar Extraction

Table 1 provides a summary of chemical analysis of the liquor resultingfrom hemicellulose sugar extraction of various biomass types. The %monomeric sugar is expressed as % weight out of total sugars weight. Allother results are expressed as % weight relative to dry biomass.

All treatments were carried out in a 0.5 L pressure reactor equippedwith a stirrer and heating-cooling system. The reactor was charged withthe biomass and the liquid at amounts given in the table. The reactorwas heated to the temperature indicated in the table, time count wasstarted once the reactor reached 5° C. below the designated temperature.Once the time elapsed, the reactor was cooled down. Solid and liquidwere separated, and the content of the obtained liquor was analyzed, alldata was back calculated relative to dry biomass weight. HPLC methodswere applied to evaluate % Total Sugars in the liquor, % monomericsugars and % Acetic Acid. The % Degradation product is the sum of %Furfurals (GC or HPLC analysis), % Formic acid (HPLC) and % Levullinicacid (HPLC). Acid Soluble Lignin was analyzed according to NRELTP-510-42627 method.

TABLE 1 Treatment conditions and chemical analysis of the resultingliquor Biomass Acid % Degradation Ref Biomass Dry Soln. (s) con. Time, %TS¹/ % DP1³/ % AcOH⁴/ Products⁵/ % ASL/ # Type wt, g wt. % wt T ° C. minDB² % TS DB DB DB 9114 Eucalyptus 45.2 198.2 0.7⁶ 140 40 22.4 NA 1.7 NANA   5a Eucalyptus 33.2 199.5 0.7⁶ 135  90 60  60 21.8 91 3.6 1.3 3.59004 Acacia 33.7 201.8 0.7⁶ 145 40 21.2 79 3.3 0.9 2.6 9012 Leucaena34.1 201.3 0.7⁶ 145 60 22.0 96 3.4 1.3 2.0 9018 EFB 34.6 203.8 0.7⁶ 14540 25.2 79 1.3 0.7 1.2 9019 Bagasse 13.3 194.8 0.7⁶ 145 40 29.8 96 2.50.7 2.5 YHTp83/15 Pine 18.1 190.5 0.7⁷ 160 15 22.9 95 0.07 1.5 0.9 ¹%Total Sugars (% TS) measured by HPLC in the liquor ²DB—Dry Biomass ³%Monomers out of total dissolved sugars measured by HPLC in the liquor ⁴%Acetic Acid measured by HPLC in the liquor ⁵% Degradation Products = %Furfurals + % Formic Acid + % Levullinic Acid. % Furfurals measured byGC or HPLC, % Formic acid and % Levullinic acid measured by HPLC ⁶0.5%H₂SO₄ + 0.2% SO₂ ⁷0.7% H₂SO₄ + 0.03% Acetic acid

Example 2—Large Scale Chemical Analysis of Lignocellulose Matter afterHemicellulose Sugar Extraction

Table 2 provides a summary of chemical analysis of various types ofbiomass after hemicellulose sugar extraction.

Pine (ref A1202102-5): Fresh Loblloly pine chips (145.9 Lb dry wood)were fed into a Rapid Cycle Digester (RDC, Andritz, Springfield, Ohio.An acid aqueous solution (500 Lb) was prepared by adding 0.3% H₂SO₄ and0.2% SO₂ to water in a separate tank. The solution was heated to 135 Cand then added to the digester to cover the wood. The solution wascirculated through the wood for 40 minutes while maintaining thetemperature. After 60 minutes, the resulting liquor was drained to aliquor tank and using steam the wood was blown to a cyclone to collectthe wood (128.3 Lb dry wood) and vent the vapor. The extracted wood wasanalyzed for sugar content, carbohydrate composition, ash, elements (byICP), and DCM extractives. The analyses of the hemi depletedlignocellulose material show extraction of 42.4% Arabinan, 10.5%Galactan, 9.6% Xylan, 14.3% Manan, and 11.8% Glucan, indicating thatmostly hemicellulose is extracted. Analyses also show 11.6% of “others”,including ASL, extractives and ash. The overall fraction ofcarbohydrates in the remaining solid is not different within the errorof the measurement to that of the starting biomass due to this removalof “others”. It is however easily notices that the extracted woodchipsare darker in color and are more brittle than the fresh biomass.

Pine (ref A1204131-14(K1)): Fresh Loblloly pine chips (145.9 Lb drywood) were fed into a Rapid Cycle Digester (RDC, Andritz, Springfield,Ohio. An acid aqueous solution (500 Lb) was prepared by adding 0.3%H₂SO₄ and 0.2% SO₂ to water in a separate tank. The solution was heatedto 135 C and then added to digester to cover the wood. The solution wascirculated through the wood for 180 minutes while maintaining thetemperature. After 180 minutes, the resulting liquor was drained to aliquor tank and using steam the wood was blown to a cyclone to collectthe wood (121.6 Lb dry wood) and vent the vapor. The material wasanalyzed as described above. The analyses of the hemi depletedlignocellulose material show extraction of 83.9% Arabinan, 84.3%Galactan, 50.1% Xylan, 59.8% Manan and no extraction of glucan,indicating effective extraction of hemicellulose. Analyses also showextraction of 21.8% of “others” including lignin, extractives and ash.

Eucalyptus (ref A120702K6-9): Fresh Eucalyptus Globulus chips (79.1 Kgdry wood) were fed into a Rapid Cycle Digester (RDC, Andritz,Springfield, Ohio). An acid aqueous solution was prepared by adding 0.5%H₂SO₄ and 0.2% SO₂ to water in a separate tank. The solution was heatedto 145° C. and then added to digester to cover the wood. The solutionwas circulated through the wood for 60 minutes while maintaining thetemperature, then heating was stopped while circulation continued foranother 60 minute, allowing the solution to cool. After 120 minutes, theresulting liquor was drained to a liquor tank and using steam the woodwas blown to a cyclone to collect the wood (58.8 Kg dry wood) and ventthe vapor. The material was analyzed as described above. Analyses showedthat 20.1% of the carbohydrates were extracted from the wood (dry woodbase) xylose containing 70% of these sugars, 91% of the sugars in theliquor present as monomers. Under these conditions acetic acidconcentration in the liquor was 3.6% (dry wood base) showing maximalremoval of acetate groups from hemicellulose sugars; 4.2% (dry woodbase) of acid soluble lignin. These results indicate effectiveextraction of hemicellulose and in particularly xylose, along withhydrolysis of the acetate groups from substituted xylosans. At the sametime a significant amount of acid soluble lignin, extractives and ashare also extracted into the liquor.

TABLE 2 Chemical analysis of lignocellulose matter after hemicellulosesugar extraction % Total DCM Biomass Ash Ca Na Mg K % % % % % Carbo-Extrac- Ref Type % wt ppm ppm ppm ppm Arabinan Galactan Glucan XylanMannan hydrate tives A1202102- Pine 0.59 248 NA 123 92 0.25 1.33 48.134.75 8.48 62.94 NA 5¹ A1204131- Pine 0.31 113 388 44 23 0.21 0.38 51.683.14 4.89 60.30 1.07 14(K1)² A120702K6- Eucalyptus 0.35 95 109 30 72<0.01 0.03 67.48 2.13 0.20 69.54 0.26 9³ ¹Hemicellulose sugarextraction: 135° C. for 60 minutes, 0.3% H₂SO₄, 0.2% SO₂. ²Hemicellulosesugar extraction: 135° C. for 180 minutes, 0.3% H₂SO₄, 0.2% SO₂.³Hemicellulose sugar extraction: 145° C. for 60 minutes + cool down 60minutes, 0.3% H₂SO₄, 0.2% SO₂.

Example 3—Direct Lignin Extraction

After hemicellulose sugars were extracted from eucalyptus chips, theremainder was mainly cellulose and lignin. The remainder was delignifiedusing an aqueous organic solution containing acetic acid according tothe process described below.

Eucalyptus wood chips (20.0 g) were mixed with a solution of 50/50 v/vof methylethylketone (MEK) and water that contains 1.2% acetic acid w/wof solution at a ratio of 1:10 (100 mL water, 100 mL MEK, and 2.2 gacetic acid). The mixture was treated at 175° C. for 4 hours in anagitated reactor. Then the system was allowed to cool to 30° C. beforethe reactor is opened. The slurry was decanted and the solid iscollected for further analysis.

After the reaction, there was 127 g free liquid, of which 47.2 g organicand 79.8 g aqueous. The organic phase contained 1.1 g acetic acid, 10.4g water, and 5.5 g dissolved solids (0.1 g sugars and 5.4 g others,which is mainly lignin). The aqueous phase contained 1.4 g acetic acid,2.1 g dissolved solids (1.5 g sugars and 0.6 g other).

After decanting of the liquid, black slurry and white precipitate wereat the bottom of the bottle. This material was vacuum-filtered andwashed thoroughly with 50/50 v/v MEK/water (119.3 g MEK 148.4 g water)at room temperature until the color of the liquid became very paleyellow. Three phases were collected; organic 19.7 g, aqueous 215 g, andwhite solid 7 g dry. The organic phase contained 0.08 g acetic acid and0.37 g dissolved solids. The aqueous phase contained 0.56 g acetic acidand 0.6 g dissolved solids.

All organic phases were consolidated. The pH of the solution is adjustedto pH 3.8. The solution was then allowed to separate into an aqueousphase (containing salts) and an organic phase (containing lignin). Thelignin-containing organic phase was recovered and purified using astrong acid cation column. The organic solution was then added drop-wiseinto an 80° C. water bath to precipitate the lignin.

¹³C Solids State NMR analysis of the white precipitate indicates that itcomprises mostly cellulose (pulp). The amount of lignin is notdetectable. The reaction is successful in delignifying the eucalyptuswood chips.

Example 4—Analyses of Ash of Louisiana Bagasse Feedstock Before andafter Soil and Ash Removal

The ash fraction of a sample of bagasse taken from a pile at a sugarmill in Louisiana was evaluated by ashing of samples in a microwavefurnace (3.1. CEM Phoenix™ Microwave Muffle Furnace), and was found tocontain 13.4% ash.

TABLE 3A Ash results after different treatments to remove soil and ashSample % Ash Louisiana Sample R1 13.12 Louisiana Sample A 17.81Louisiana Sample R2 13.38 Sample R1 washed with water 12.78 Sample Awashed with water 17.16 Sample R2, 1 shear treatment, 1 pressure wash6.67 Sample A, 2 shear treatments, 2 pressure wash 2.52 Sample R2, 6shear treatments, 6 pressure wash 2.68 Sample R2, 8 shear treatments, 8pressure wash 2.26

The results summarized in the table demonstrate the high ash present inLouisiana bagasse obtained from different sugar mills and differentsampling times. The results also show that to achieve effective removalof soil and ash it is essential to apply several cycles of sheartreatment and washing with high pressure to cause the removal of stones,sand and sols of ash compound. The remaining bagasse still holds 2-3% of“true” ash, that is related to metal cations and other elementsassociated at molecular level in the cell structure.

B) Bagasse was milled and de-ashed, samples before and after de-ashingwas sieved through a series of screens:

TABLE 3B De ashing of bagasse Ground Raw Bagasse De-Ashed Bagasse ScreenScreen Fiber Fiber Size Size, mm % Length, mm % Length, mm on 6 mesh 3400.3 1.0-15.0 0 on 12 mesh 170 5 2.0-15.0 1 5.0-10.0 on 16 mesh 120 9.51.0-10.0 5.4 2.0-10.0 on 20 mesh 80 12.7 1.0-10.0 6 1.0-5.0  on 30 mesh60 57.3 <1.0-5.0  71.1 1.0-5.0  thru 30 mesh <60 15.4 <1.0 16.5 <1.0

The table demonstrates that ability to remove by industrial means mostof the soil and ash from bagasse feedstock by shear treatment and highpressure wash, while still maintaining ˜85% of the original feedstock atsize greater than 30 mesh, that allows further handling of the washedmaterial.

Example 5—Hydrolysis of Cellulose by Cellulase

Cellulose pulp (eucalyptus pulp) was obtained as the remainder after thehemicellulose and lignin extraction. Cellulose pulp suspension having10-20% solids in 0.05M acetate buffer, pH 4.55, 5%/cellulose,cellulase:cellobiase 1:1 was prepared. The suspension was stirred at 55°C. Samples of the liquor were taken periodically for analysis of thedissolved sugars. The dissolving sugars were mostly glucose, but canalso include some residual hemicellulose sugars remaining in the pulp.The dissolved sugar contained 7.78% lignin and 94.22% holocellulose,(89.66% glucose). As % solids increased, overall yield decreased (solong as the enzyme loading is the same). However the yield was highercompared to a reference sample hydrolyzed under the same conditionsusing Sigmacell (Sigma # S5504 from cotton linters, type 50, 50 um), asseen in FIG. 8B. the cellulose pulp is well saccharified by thecellulase mix enzyme (although it still contains some residual lignin).the reaction rate of E-HDLM is higher than the reference material

Example 6—Characterization of Remainder Cellulose

Eucalyptus feedstock was treated to extract hemicellulose sugars, ashand acid soluble lignin as described in example 2. The lignocellulosicremainder was milled to produce powder of ca. 1400 micron. The milledpowder (˜20 g, 5% moisture) was loaded in a pressure reactor. 100 gwater and 80 g methylethyl ketone were added to the reactor, and aceticacid 0.5% to 2.5% wt/wt to total liquids. The reactor was heated to160-190° C. for 1-3 hours. The reactor was cooled down, solid and liquidseparated. The solid was washed with additional amount of watersaturated MEK solution, and dried under vacuum.

The amount of cellulose and lignin in the remainder solid was measuredaccording to NREL/TP-510-42618.

Remainder Time Temperature % Solid (g/100 % % (h) (° C.) AcOH g initialsolid) Lignin Cellulose 2 175 2.5 54.7 2.1 96.2 1 190 0.5 54.2 10.6 80.43 160 0.5 60.5 7.5 87.6

The results indicate high efficiency of the reaction conditions inextracting lignin, leaving behind down to less than 5% ligninweight/weight solid under optimal conditions, with as low as 2%achievable.

Example 7—Elemental Analysis of Lignin Compositions

The Elemental analysis of carbon, nitrogen, hydrogen and sulfur contentof organic material is determined by the FLASH EA 111 CHNS Analyzer.Samples were incinerated under 900° C. using He and O₂ atmosphere withflow rates of 140 ml/min and 250 ml/min respectively.

Based on elemental analysis the empiric monomer formula is calculated,assuming 9 carbon atoms in each monomer. The results for eucalyptus,pine and bagasse produced according to the method of this invention areshown in the table below.

Compared to Kraft softwood lignin, both ASE lignin and HP lignin(exemplary HP can be produced according to Section VII of PCTUS2013/039585) are significantly more pure, particularly the level ofsulfur is below detection level while Kraft has 1.6%, which is wellnoticed by is malodor in production processes involving lignin or evenin final products incorporating Kraft lignin; the ratio of O/C issignificantly lower in ASE and HP lignin compared to Kraft, i.e. it isless oxidized, therefore ASE and HP lignin are preferred startingmaterial for chemical conversions that require de-oxygenation, forexample conversion to non-oxygenated aromatic molecules.

Elemental Analysis Measurements of Lignin

% HP lignin - after HCl ASE lignin - direct extraction hydrolysis KraftElements Eucalyptus Pine Bagasse Eucalyptus Pine SW C 62.1 67.1 66.265.9 67.0 47.8 H 5.91 6.68 6.71 5.32 5.23 4.93 N 0.12 0.12 0.35 <0.05<0.05 0.1 O 27.5 23.4 23.6 28.1 22.4 25.6 S <0.2 <0.2 <0.2 <0.2 <0.21.56 Formula C₉H_(10.28)O_(2.99) C₉H_(10.75)O_(2.35) C₉H_(10.94)O_(2.40)C₉H_(8.65)O_(2.88) C₉H_(8.37)O_(2.26) C₉H_(11.02)O_(3.6) O/C 0.33 0.260.27 0.32 0.25 0.40 H/C 1.14 1.19 1.22 0.96 0.93 1.2

Example 8—Determination of Lignin Functional Groups by ³¹P NMR

Quantitative ³¹P NMR were acquired on dry lignin (˜40 mg) dissolved in500 μL of a mixture consisting of 1.6:1 (v/v) deuterated pyridine(Py-D₅)/deuterated chloroform (CDCl₃).Endo-N-Hydroxy-5-norbornene-2,3-dicarboximide (e-HNDI) is used as aninternal standard, where 200 μL of 50.0 mmol/L in Py-D₅/CDCl₃ (1.6/1,v/v) is added. Also, 50 μL of chromium (III) acetylacetonate solution(11.4 mg/mL in Py-D₅/CDCl₃ (1.6/1, v/v)) is added as a relaxation agent.The dissolved lignin is then derivatized with 100 μL of2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP). The spectrumwas acquired using an inverse gated decoupling pulse sequence, 75° pulseangle, 10 s pulse delay, 150 scans, zero filling, 1.0 Hz linebroadening, and at 25° C. Spectra collected according to this method forthe 3 feedstocks and the reference Kraft sample are presented in FIG.11. FIG. 11A is lignin derived from the Kraft process, FIG. 11B islignin derived from pine, FIG. 11C is lignin derived from bagasse, andFIG. 11D is lignin derived from eucalyptus. The integrations of thepeaks are listed in the table below.

Phenolic OH (mmol/g lignin Syringyl and Guaiacyl and/or Condensedp-hydroxyphenyl Aliphatic OH Phenolic OH Phenolic OH Carboxylic OH(mmol/g (mmol/g (mmol/g (mmol/g Species lignin) lignin) lignin) Totallignin) ASE 1.73 3.04 0.68 3.72 0.08 Eucalyptus ASE Pine 1.99 1.14 1.883.02 0.30 ASE Bagasse 1.00 1.29 1.70 2.99 0.35 HP 0.31 1.72 1.52 3.240.46 Eucalyptus HP Pine 0.35 2.9 2.9 0.91 Kraft SW 2.03 1.43 1.92 3.350.46 Kraft Black 1.87 1.28 1.72 3.0 0.41 Liquor Lignin SW

Example 9—Determination of Lignin Functional Groups by ¹³C NMR

Quantitative ¹³C NMR spectrum is acquired using DMSO-D6 (500 μL) assolvent for lignin (80 mg), with an inverse gated decoupling sequence,90° pulse angle, 12 s pulse delay, and about 10000 scans.

Reference^(#) ASE Lignin (direct HP lignin (after Residual extraction)HCl hydrolysis Pine Kraft Eucalyptus Pine Bagasse Eucalyptus Pine EOLSoftwood Degree of 0.6 0.8 0.4 0.9 0.9 1.1 1 condensation Methoxylcontent 1.3 0.8 0.9 0.8 0.7 0.9 0.8 (#/aryl group) Aliphatic linkages0.5 0.1 0.2 0.2 0.1 0.3 0.3 (β-O-4′) (#/aryl group) Aromatic C—O 2.0 1.91.7 1.9 1.8 2.1 2.1 (#/aryl group) Aromatic C—C 2.1 2.0 2.2 2.3 2.2 2.11.9 (#/aryl group) Aromatic C—H 1.9 2.2 2.1 1.7 2.1 2 2.0 (#/aryl group)^(#)“Lignin structural modifications resulting from ethanol organosolvtreatment of loblolly pine”. Ragauskas A J, Energ Fuel 2010; 24 (1):683-689.

The data in the table shows that lignin of the current invention haslower degree of condensation than lignins produces through otherprocesses such as the Organosolv process or Kraft milling.

Example 10—ICP, Ash and Carbohydrate Measurements of Lignin Samples

Inductively coupled plasma (ICP) analysis of bagasse lignin, ashanalysis according to NREL method TP-510-42622 and carbohydrate analysisaccording to NREL method TP-510-42618 are provided below:

Concentration (ppm) Bagasse Eucalyptus Pine Element (ref: 18740) (ref:16028) (ref: 16032) S 660 690 538 Ca <10 14 4 Fe 50 343 264 K <10 33 43Mg <10 9 10 Na <10 <2 <2 Ash 0.1% NA NA Carbohydrate 0.1% NA NA

Notably, the small amount of carbohydrate found comprise glucose only.Also, the analysis of lignocellulose composition by TP 510-42618 showsthat >90% of the lignin to be Klason lignin.

Example 11—Solubility of Lignin in Various Solvents

Solubility of various types of high purity lignins in simple solvents atroom temperature is provided below:

Methylethyl 0.1N DMSO THF Toluene ketone NaOH Pine >120 g/L >40 g/LInsoluble Insoluble >10 g/L Eucalyptus >120 g/L >40 g/L InsolubleInsoluble >10 g/L Bagasse >120 g/L >40 g/L Insoluble Insoluble >10 g/L

Example 12—Evaluation of Thermal Properties of Lignin by TGA and DSC

The table below provides weight loss values of pine, eucalyptus andbagasse lignin samples as measured by Thermal Gravimetric Analysis. Apre-heating cycle was applied to remove moisture.

TGA Profiles of Lignin Samples

Eucalyptus Bagasse Pine Moisture 0 (Wt/%) 0 (Wt/%) 0.2 (Wt/%) 5%Degradation 250 (° C.) 230 (° C.) 230 (° C.) 10% Degradation 300 (° C.)280 (° C.) 270 (° C.) Char 36.2 (Wt/%) 33.4 (Wt/%) 33.6 (Wt/%)

DSC was performed according to DIN 53765: the sample is first dried by apre-heat cycle. Then, 2 consecutive heat cycles are measured, typicallyin the first cycle annealing processes take place that affect thepolymer structure, while in the second cycle the major transition Tg isascribed to the glass transition of the polymer. Typically, Tg value ofthe second cycle is elevated by 4 to 30° C. Table 7b provides values of1^(st) and 2^(nd) cycle measurements of Tg and the difference betweenthe two cycles.

TABLE 7b Tg values of lignin samples Tg (1) ° C. Tg (2) ° C. ΔTg ° C.ASE Pine 91 105 14 ASE Eucalyptus 131 150 19 ASE Bagasse 110 129 19

Example 13—High Purity of Lignin Solution as Feed for Lignin ConversionProcesses

A high purity lignin solution in water saturated MEK is made accordingto example 3. This composition of water saturated MEK comprises 1-8,2-6, 2, 2.5-5% wt/wt dissolved lignin, less than 1, 0.5, 0.2, 0.1%acetic acid, less than 1000, 500, 250, 200 ppm other organic acid, lessthan 500, 250, 100 ppm ash, less than 500, 250, 100, 50, 25 ppmcarbohydrate oligomers, less than 50, 25, 10, 5, 2 ppm furfurals, lessthan 50, 25, 10, 5, 1, 0.5 ppm sulfuric acid.

This composition is used as feed for lignin conversion processes. Thiscomposition of highly refined lignin soluble in low boiling pointsolvent is particularly suitable as feed for conversion processes thatbreak the lignin polymer to small molecules, including phenols,guaiacols, syringols, eugenol, catechols, vanillin, vanillic acid,syringaldehyde, benzene, toluene, xylene, styrene, biphenyls andcyclohexane.

Example 14—Characterization of Remainder Cellulose Prepared fromLouisiana Bagasse

Bagasse was washed and extracted according to example 1 to extracthemicellulose. The remaining lignocellulose matter was then heated to210° C. for 2.5-3 hours in a solution comprising 1:1 MEK: water, furthercomprising 0.3% wt/wt acetic acid. The remaining pulp was collected,washed with water-saturated MEK and dried.

The composition of resulting cellulose pulp obtained was characterizedaccording NREL method TP-510-42618. Ash was determined according to NRELmethod TP-510-42622. Sigmacell cellulose and Whatman No. 1 paper areused as reference cellulose material. The composition of the bagassefeed was analyzed by the same methods. The results are summarized in thetable below.

Composition of the Remaining Cellulose Pulp, Feedstock Bagasse andComparative Cellulose Samples

C6 sugars (glucose) Total Sample % wt/wt C5 sugars sugars Lignin Ash(ref) (% wt/wt) % wt/wt % wt/wt % wt/wt % wt/wt Remaining 85.4 (84.2)1.6 97.0 4.6 NA pulp (13650) Remaining 83.3 (80.7) 1.5 84.8 7.8 NA pulp(13844) Remaining 75.7 1.0 76.7 10.9 12.4 pulp (J01) Bagasse 30.6 (29.1)18.9 49.5 19.1 22.8 (13633) Bagasse 39.2 (4235.2) 6.8 46.0 23.7 24.3(13634) Sigmacell 84.5 (80.2) 3.0 87.5 NA NA Whatman 86.8 (84.6) 1.688.4 NA NA paper No 1

The remaining cellulose pulp was also analyzed for inorganic impuritiesby ICP-AES, the results are provided below.

ICP results of remaining cellulose pulp Ppm Element Sample 13633 Sample13644 Ca 270 401 Cu 5 48 Fe 143 66 K 72 98 Mg 6 <2 Mn 2 <2 Na 6 <2 Al 8216 Zn 2 3 Cr 32 192

Example 15: Composition of the Remaining Cellulose Pulp Made from Pineand Eucalyptus

Pine and eucalyptus feedstocks were treated to extract hemicellulosessugars according to the procedure of example 1. The remaininglignocellulose matter was then heated to 160-210° C. for 1-3 hours in asolution comprising 1:1 MEK: water, further comprising 0.5-1.5% wt/wtacetic acid. The remaining pulp was collected, washed withwater-saturated MEK and dried. The composition of resulting cellulosepulp obtained was characterized according NREL method TP-510-42618. Ashwas determined according to NREL method TP-510-42622.

Composition of the Remaining Cellulose Pulp

C6 sugars (glucose) Total Sample % wt/wt C5 sugars sugars Lignin Ash(ref) (% wt/wt) % wt/wt % wt/wt % wt/wt % wt/wt Eucalyptus 57.0 (53.2)3.8 60.8 18.23 0.11 (60 min@ 160 C., 0.5% acid) (18789) Eucalyptus 70.7(66.8) 3.8 73.8 11.35 0.1 (180 min@ 160 C., 0.5% acid) (18790) Pine 52.6(47.3) 4.1 56.7 37.43 0.39 (60 min@ 170 C., 0.5% acid) (18791) Pine 63.4(60.5) 1.5 64.9 23.8 0.52 (120 min@ 200 C., 1.5% acid)

Remaining Cellulose Pulps Obtained Through this Process were Analyzed byICP

Sample reference Species S Ca Fe K Mg Na 16995 Eucalyptus 400 150 160 4020 30 16998 Eucalyptus 430 110 100 30 6 10 18104 Pine 530 40 130 150 8010 18116 Pine 400 40 200 70 20 2

Example 16—Solubility Properties of Remainder Cellulose Pulps

The pulps were characterized for their solubility in water and ether, incomparison to Avicel PH-200, the results are summarized in the tablebelow.

Water Water Ether soluble soluble soluble Conduc- sub- sub- sub- tivitystances stances stances LIMS PH μS/cm % mg/5 gr mg/10 gr Avicel Liter-5.5-7  75 0.25 12.5 5 PH-200 ature* Bagasse 17558 5.7-6.4 15-30 0.2110.7 19.6 Pine 18578 4.4-4.6 35-50 0.19 9.7 19.8 Euca- 16995 4.2-4.545-65 0.25 12.7 2.2 lyptus *Published online:http://www.signetchem.com/downloads/datasheets/Fmc-biopolymer/Avicel-Ph-200-Specifications.pdf

Example 17—Determination of Marker Molecules of Pine Derived LigninSample by GCMS

A sample of pine derived lignin was preparation according to example 3.The conditions used for this sample was 230° C., 3 h, 0.5% acetic acid.The refined MEK solution comprising lignin (i.e. just before flashevaporation) was injected into the gas chromatogram (GC). GC-MSconditions were as follows: Column (HP-5MS 30m); Temp. program (2.5, 70,1, 10, 320, 10); Split (14:1), and the identification of peaks was donewith the help of NIST Mass Spectral Search Program Version 2.0d. Thesamples were injected twice—first time with low sensitivity(chromatogram shown in FIG. 12A), to locate the retention time of thesolvents. The second injection was done at high sensitivity(chromatogram shown in FIG. 12B), and the solvent peaks were notobserved by MS to avoid an overload of the instrument. The syringe waswashed with methanol, and some or all of the methanol in thechromatogram could be an artifact from cleaning of the syringe. Themarker molecules and volatile contents of the lignin composition areshown in the table below.

Pine 230° C./3 h/0.5%

Peak R.T. Pct Total Substance 1 1.364 0.925 Nitrogen 2 1.402 36.611Methanol (artifact of column cleaning) 3 1.475 1.033 Acetone 4 1.5560.765 Acetic acid 5 1.615 51.164 Methylethyl ketone (MEK) 7 1.826 0.335Methylpropenyl ketone

Pct Area (excl. Peak R.T. solvents) Substance  1 2.605 0.805

 2 2.763 0.871

 7  8 3.676 3.761 1.5 3.166

10 4.148 2.927

11 4.192 2.804

12 4.259 5.06

14 4.548 4.917

21 5.865 1.391

27 6.618 1.46

28 6.295 1.083

39 8.522 3.843

46 9.537 1.673

49 10.018 5.06

51 10.154 0.89

58 10.916 0.601

86 20.793 0.431

Example 18—Determination of Marker Molecules of Bagasse Derived LigninSample by GCMS

A sample of Bagasse derived lignin was preparation according to example3 and 4. The conditions used for this sample was 200° C., 2.6 h, 0.3%acetic acid. The refined MEK solution comprising lignin (i.e. justbefore flash evaporation) was injected into the gas chromatogram (GC).GC-MS conditions were as follows: Column (HP-5MS 30m); Temp. program(2.5, 70, 1, 10, 320, 10); Split (14:1), and the identification of peakswas done with the help of NIST Mass Spectral Search Program Version2.0d. The samples were injected twice—first time with low sensitivity(chromatogram shown in FIG. 13A), to locate the retention time of thesolvents. The second injection was done at high sensitivity(chromatogram shown in FIG. 13B), and the solvent peaks were notobserved by MS to avoid an overload of the instrument. The syringe waswashed with methanol, and some or all of the methanol in thechromatogram could be an artifact from cleaning of the syringe. Themarker molecules and volatile contents of the lignin composition areshown in the table below.

Pct Area (excl. Peak R.T. solvents) Substance  1 2.764 12.322

 3 3.041 1.72

 4 3.757 1.597

 5 3.914 0.883

 6 4.144 3.246

 7 4.188 4.117

 8 4.254 6.487

 9 4.398 1.173

10 4.543 9.498

14 7.6 21.551

15 7.741 5.208

17 9.006 2.847

21 10.141 1.595

25 13.299 2.578

26 14.548 1.669

28 20.566 2.181

Example 19—Determination of Marker Molecules of Eucalyptus DerivedLignin Sample by GCMS

A sample of Eucalyptus derived lignin was preparation according toexample 3. The conditions used for this sample was 170° C., 1.0 h, 0.5%acetic acid. The refined MEK solution comprising lignin (i.e. justbefore flash evaporation) was injected into the gas chromatogram (GC).GC-MS conditions were as follows: Column (HP-5MS 30m); Temp. program(2.5, 70, 1, 10, 320, 10); Split (14:1), and the identification of peakswas done with the help of NIST Mass Spectral Search Program Version2.0d. The samples were injected twice—first time with low sensitivity(chromatogram shown in FIG. 14A), to locate the retention time of thesolvents. The second injection was done at high sensitivity(chromatogram shown in FIG. 14B), and the solvent peaks were notobserved by MS to avoid an overload of the instrument. The syringe waswashed with methanol, and some or all of the methanol in thechromatogram could be an artifact from cleaning of the syringe. Themarker molecules and volatile contents of the lignin composition areshown in the table below.

Pct Area (excl. Peak R.T. solvents) Substance  1 2.77 25.186

 2 3.06 2.231

 4 3.757 1.187

 9 4.542 1.673

13 7.735 3.488

14 8.123 2.154

18 9.512 3.736

19 10.139 1.445

20 10.901 1.638

25 13.313 12.219

26 13.794 3.873

27 14.046 0.587

32 15.094 2.761

36 16.521 3.343

38 16.673 2.125

44 27.009 1.275

¹Lipid and lignin composition of woods from different eucalypt species;Jorge Rencoret, Ana Gutie′ rrez and Jose′ C. del R1′o; Holzforschung,Vol. 61, pp. 165-174, 2007

1.-77. (canceled)
 78. A product comprising a lignin composition having adegree of condensation of less than 0.9 and characterized by at leasttwo characteristics selected from the group consisting of: (i) ligninaliphatic hydroxyl group in an amount up to 2 mmole/g; (ii) at least 2.5mmole/g lignin phenolic hydroxyl group; (iii) less than 0.40 mmole/glignin carboxylic hydroxyl group; (iv) sulfur in an amount up to 1%weight/weight; (v) nitrogen in an amount up to 0.5% weight/weight; (vi)5% degradation temperature higher than 220° C.; (vii) 10% degradationtemperature higher than 260° C.; (viii) less than 1% ash weight/weight;(ix) a formula of C_(a)H_(b)O_(c); wherein a is 9, b is less than 12 andc is less than 3.5; (x) a methoxyl content of at least 0.8; (xi) an O/Cweight ratio of less than 0.4; and (xii) a glass transition elevationbetween a first and a second heat cycle as measured by differentialscanning calorimetry according to DIN 53765 in the range of 10 to 30° C.79. The product of claim 78, comprising one or more other ingredients.80. The product of claim 79, wherein the product is selected from thegroup consisting of: carbon fibers, protective coatings,lignosulfonates, pharmaceuticals, dispersants, emulsifiers, complexants,flocculants, agglomerants, pelletizing additives, resins, adhesives,binders, absorbents, toxin binders, films, rubbers, elastomers,sequestrants, solid fuels, paints, dyes, plastics, wet spun fibers, meltspun fibers and flame retardants.
 81. The product of claim 79, whereinthe product is selected from the group consisting of: a non-wovenfabric, a woven fabric, insulation material, sports equipment,automotive parts, airplane or helicopter parts, boat hulls or portionsthereof and loudspeakers.
 82. The product of claim 78, wherein theproduct is provided as fibers.
 83. The product of claim 82, wherein acomposite material comprises a polymer reinforced with the fibers andone or more materials selected from the group consisting of epoxy resin,polyester, polyvinyl ester and nylon.
 84. A method of spinning fibers,comprising: (a) providing a lignin composition having a degree ofcondensation of less than 0.9 and characterized by at least twocharacteristics selected from the group consisting of: (i) ligninaliphatic hydroxyl group in an amount up to 2 mmole/g; (ii) at least 2.5mmole/g lignin phenolic hydroxyl group; (iii) less than 0.40 mmole/glignin carboxylic hydroxyl group; (iv) sulfur in an amount up to 1%weight/weight; (v) nitrogen in an amount up to 0.5% weight/weight; (vi)5% degradation temperature higher than 220° C.; (vii) 10% degradationtemperature higher than 260° C.; (viii) less than 1% ash weight/weight;(ix) a formula of C_(a)H_(b)O_(c); wherein a is 9, b is less than 12 andc is less than 3.5; (x) a methoxyl content of at least 0.8; (xi) an O/Cweight ratio of less than 0.4; and (xii) a glass transition elevationbetween a first and a second heat cycle as measured by differentialscanning calorimetry according to DIN 53765 in the range of 10 to 30°C.; (b) spinning said lignin to produce fibers; and (c) de-solventizingsaid fibers.
 85. The method of claim 84, further comprising contactingsaid composition with an anti-solvent.
 86. The method of claim 84,further comprising mixing said composition with a synthetic polymericmaterial.
 87. The method of claim 86, wherein said synthetic polymericmaterial comprises polyacrylonitrile.
 88. The method of claim 86,wherein a ratio of lignin:synthetic polymer is ≧1:10.
 89. The method ofclaim 86, wherein a ratio of lignin:synthetic polymer is ≦10:1.
 90. Themethod of claim 84, further comprising carbonizing said fibers toproduce carbon fibers.
 91. A method comprising: (a) providing a lignincomposition having a degree of condensation of less than 0.9 andcharacterized by at least two characteristics selected from the groupconsisting of: (i) lignin aliphatic hydroxyl group in an amount up to 2mmole/g; (ii) at least 2.5 mmole/g lignin phenolic hydroxyl group; (iii)less than 0.40 mmole/g lignin carboxylic hydroxyl group; (iv) sulfur inan amount up to 1% weight/weight; (v) nitrogen in an amount up to 0.5%weight/weight; (vi) 5% degradation temperature higher than 220° C.;(vii) 10% degradation temperature higher than 260° C.; (viii) less than1% ash weight/weight; (ix) a formula of C_(a)H_(b)O_(c); wherein a is 9,b is less than 12 and c is less than 3.5; (x) a methoxyl content of atleast 0.8; (xi) an O/C weight ratio of less than 0.4; and (xii) a glasstransition elevation between a first and a second heat cycle as measuredby differential scanning calorimetry according to DIN 53765 in the rangeof 10 to 30° C.; and (b) converting at least a portion of lignin in thecomposition to a conversion product.
 92. The method of claim 91, whereinthe converting comprises treating with hydrogen.
 93. The method of claim91, wherein the converting comprises treating with a hydrogen donor. 94.The method of claim 93, wherein the hydrogen donor is selected fromformic acid, formate salt, and an alcohol.
 95. The method of claim 94,wherein the alcohol is isopropanol.
 96. The method of claim 91, furthercomprising producing hydrogen from lignin.
 97. The method of claim 91,wherein the conversion product comprises at least one item selected fromthe group consisting of bio-oil, carboxylic and fatty acids,dicarboxylic acids, hydroxyl-carboxylic, hydroxyl di-carboxylic acidsand hydroxyl-fatty acids, methylglyoxal, mono-, di- or poly-alcohols,alkanes, alkenes, aromatics, aldehydes, ketones, esters, phenols,benzene, toluenes, and xylenes.
 98. The method of claim 91, wherein theconversion product comprises a fuel or a fuel ingredient.
 99. The methodof claim 91, wherein the conversion product comprises para-xylene. 100.The method of claim 91, wherein at least a portion of a consumer productis the conversion product.
 101. The method of claim 100, wherein theconsumer product comprises at least one chemical selected from the groupconsisting of lignosulfonates, bio-oil, carboxylic and fatty acids,dicarboxylic acids, hydroxyl-carboxylic, hydroxyl di-carboxylic acidsand hydroxyl-fatty acids, methylglyoxal, mono-, di- or poly-alcohols,alkanes, alkenes, aromatics, aldehydes, ketones, esters, biopolymers,proteins, peptides, amino acids, vitamins, antibiotics, paraxylene andpharmaceuticals.
 102. The method of claim 100, wherein the consumerproduct comprises para-xylene.
 103. The method of claim 100, wherein theconsumer product is selected from the group consisting of dispersants,emulsifiers, complexants, flocculants, agglomerants, pelletizingadditives, resins, carbon fibers, active carbon, antioxidants, flameretardant, liquid fuel, aromatic chemicals, vanillin, adhesives,binders, absorbents, toxin binders, foams, coatings, films, rubbers andelastomers, sequestrants, fuels, and expanders.
 104. The method of claim100, wherein the consumer product is used in an industry selected fromthe group consisting of food, feed, materials, agriculture,transportation and construction.
 105. The method of claim 100, whereinthe consumer product has a ratio of carbon-14 to carbon-12 of about2.0×10⁻¹³ or greater.
 106. The method of claim 100, wherein the consumerproduct comprises an ingredient produced from a raw material other thanlignocellulosic material.
 107. The method of claim 106, wherein theconversion product and the ingredient are essentially of the samechemical composition.
 108. The method of claim 100, wherein the consumerproduct comprises a marker molecule at a concentration of at least 100ppb.
 109. The method of claim 108, wherein the marker molecule isselected from the group consisting of furfural and hydroxy-methylfurfural, 2,3,5 trimethyl furan, products of their condensation, colorcompounds, acetic acid, p-hydroxyphenoxyacetic acid,4-hydroxy-3,5,-dimethoxyphenyl) acetic acid, methylethyl ketone,methylpropenyl ketone, 3-(2-furyl)-3-penten-2-one,3-methyl-2-penten-4-one, 3,4-dimethyl-4-hexene-one,5-ethyl-5-hexene-3-one, 5-methyl-4-heptene-3-one, o-hydroxyanisole,3-ethyl-4-methyl-3-penten-2-one, 3,4,4-trimethyl-2-cyclohexene-1-one,2′-hydroxy-4′,5′-dimethyl acetophenone,1-(4-hydroxy-3-methoxyphenyl)propane methanol, galacturonic acid,dihydroabietic acid, glycerol, fatty acids and resin acids.